4-cycloalkyl or 4-aryl substituted phenoxyphenylamidines and use thereof as fungicides

ABSTRACT

The present invention relates to 4-cycloalkyl- or 4-aryl-substituted phenoxyphenylamidines of the general formula (I), to a process for their preparation, to the use of the amidines according to the invention for controlling unwanted microorganisms and also to a composition for this purpose, comprising the phenoxyphenylamidines according to the invention. Furthermore, the invention relates to a method for controlling unwanted microorganisms by applying the compounds according to the invention to the microorganisms and/or their habitat.

This application is a Divisional application of U.S. application Ser.No. 12/530,777, filed Oct. 13, 2009, which is a National StageApplication of PCT/EP2008/001864, filed Mar. 8, 2008, which claimspriority to European Application No. 07005005.9, filed Mar. 12, 2007,each of which is hereby incorporated by reference.

The present invention relates to 4-cycloalkyl- or 4-aryl-substitutedphenoxyphenylamidines of the general formula (I), to a process for theirpreparation, to the use of the amidines according to the invention forcontrolling unwanted microorganisms and also to a composition for thispurpose, comprising the phenoxyphenylamidines according to theinvention. Furthermore, the invention relates to a method forcontrolling unwanted microorganisms by applying the compounds accordingto the invention to the microorganisms and/or their habitat.

WO-A-00/046 184 discloses the use of amidines, includingN,N-dimethyl-N′-[4-(biphenyl-4-yloxy)-2,5-xylyl] formamidine, asfungicides.

WO-A-03/093 224 discloses the use of arylamidine derivatives asfungicides.

WO-A-03/024 219 discloses fungicide compositions comprising at least oneN2-phenylamidine derivative in combination with a further selected knownactive compound.

WO-A-04/037239 discloses antifungicidal medicaments based onN2-phenylamidine derivatives.

WO-A-05/089 547 discloses fungicide mixtures comprising at least onearylamidine derivative in combination with a further known fungicidallyactive compound.

WO-A-05/120 234 discloses fungicide mixtures comprising at least onephenylamidine derivative and a further selected known fungicide.

The effectiveness of the amidines described in the prior art is good butin many cases leaves something to be desired.

Accordingly, it is the object of the present invention to provideamidines having an improved fungicidal effectiveness.

Surprisingly, this object has been achieved by 4-cycloalkyl- or4-aryl-substituted phenoxyphenylamidines of the formula (I)

in which

-   R¹ is selected from the group consisting of hydrogen;    straight-chain, branched C₁₋₁₂-alkyl, C₂₋₁₂-alkenyl, C₂₋₁₂-alkynyl    groups, cyclic C₃₋₈-alkyl, C₄₋₈-alkenyl, C₄₋₈-alkynyl groups, where    in the ring system of all of the cyclic groups mentioned above one    or more carbon atoms may be replaced by heteroatoms selected from    the group consisting of N, O, P and S and all of the groups    mentioned above may be substituted by one or more groups selected    from the group consisting of —R′, —X, —OR′, —SR′, —NR′₂, —SiR′₃,    —COOR′, —CN and —CONR′₂, where R′ represents hydrogen or a    C₁₋₁₂-alkyl group, which may be substituted by one or more    heteroatoms selected from the group consisting of N, O, P and S;    -   —SH; —SR″, where R″ represents a C₁₋₁₂-alkyl group, where in the        ring system of all of the cyclic groups mentioned above one or        more carbon atoms may be replaced by heteroatoms selected from        the group consisting of N, O, P and S and all of the groups        mentioned above may be substituted by one or more groups        selected from the group consisting of —R′, —X, —OR′, —SR′,        —NR′₂, —SiR′₃, —COOR′, —CN and —CONR′₂, where R′ has the above        meanings;-   R² is selected from the group consisting of straight-chain, branched    C₁₋₁₂-alkyl, C₂₋₁₂-alkenyl, C₂₋₁₂-alkynyl groups, cyclic C₃₋₈-alkyl,    C₄₋₈-alkenyl, C₄₋₈-alkynyl groups, C₅₋₁₈-aryl, C₇₋₁₉-aralkyl and    C₇₋₁₉-alkaryl groups, where in the ring system of all of the cyclic    groups mentioned above one or more carbon atoms may be replaced by    heteroatoms selected from the group consisting of N, O, P and S and    all of the groups mentioned above may be substituted by one or more    groups selected from the group consisting of —R′, —X, —OR′, —SR′,    —NR′₂, —SiR′₃, —COOR′, —CN and —CONR′₂, where R′ has the above    meanings;-   R³ is selected from the group consisting of —CN, —SH, —SR″, —OR″,    —(C═O)—R″, straight-chain, branched C₂₋₁₂-alkyl, C₂₋₁₂-alkenyl,    C₂₋₁₂-alkynyl groups, cyclic C₃₋₈-alkyl, C₄₋₈-alkenyl, C₄₋₈-alkynyl    groups or C₅₋₁₈-aryl, C₇₋₁₉-aralkyl and C₇₋₁₉-alkaryl groups, where    in the ring system of all of the cyclic groups mentioned above one    or more carbon atoms may be replaced by heteroatoms selected from    the group consisting of N, O, P and S and all of the groups    mentioned above may be substituted by one or more groups selected    from the group consisting of —R′, —X, —OR′, —SR′, —NR′₂, —SiR′₃,    —COOR′, —CN and —CONR′₂, where R′ and R″ have the above meanings;    or in which-   R² and R³,-   R² and R¹ or-   R¹ and R³ together with the atoms to which they are attached or    together with further atoms selected from the group consisting of N,    O, P and S may form a four- to seven-membered ring which may be    substituted by R′, OR′, SR′, NR′₂, SiR′₃ groups, where R′ has the    above meanings;-   R⁴ and R⁵ independently of one another are selected from the group    consisting of hydrogen, —X, —CN, —SH, —SR″, —OR″, —(C═O)—R″,    straight-chain, branched C₁₋₁₂-alkyl, C₂₋₁₂-alkenyl, C₂₋₁₂-alkynyl    groups, cyclic C₃₋₈-alkyl, C₄₋₈-alkenyl, C₄₋₈-alkynyl groups or    C₅₋₁₈-aryl, C₇₋₁₉-aralkyl and C₇₋₁₉-alkaryl groups, where in the    ring system of all of the cyclic groups mentioned above one or more    carbon atoms may be replaced by heteroatoms selected from the group    consisting of N, O, P and S and all of the groups mentioned above    may be substituted by one or more groups selected from the group    consisting of —R′, —X, —OR′, —SR′, —NR′₂, —SiR′₃, —COOR′, —CN and    —CONR′₂, where R′ and R″ have the above meanings;-   R⁶ is selected from the group consisting of hydrogen, halogen atoms    and C₁₋₆-haloalkyl groups;-   R⁷ is selected from the group consisting of alicyclic C₃₋₁₂-alkyl,    C₄₋₁₂-alkenyl, C₄₋₁₂-alkynyl groups and C₅₋₁₈-aryl, C₇₋₁₉-aralkyl    and C₇₋₁₉-alkaryl groups, which may be substituted by one or more    groups selected from the group consisting of —R′, —X, —OR′, —SO₂—R′,    —SR′, —NR′₂, —SiR′₃, —COOR′, —CN and —CONR′₂, where R′ has the above    meanings and where the C₅₋₁₈-aryl, C₇₋₁₉-aralkyl and C₇₋₁₉-alkaryl    groups may be substituted by one or more heteroatoms selected from    the group consisting of N, O, P and S;    and their salts.

The present invention furthermore provides a process for preparing thephenoxyphenylamidines according to the invention which comprises atleast one of the following steps (a) to (j):

-   (a) reaction of nitrobenzene derivatives of the formula (III) with    4-substituted phenols of the formula (II) according to the reaction    scheme below:

-   (b) reaction of nitrophenol derivatives of the formula (V) with    4-substituted phenyl derivatives of the formula (IV) according to    the reaction scheme below:

-   (c) reaction of anilines of the formula (VII) with 4-substituted    phenols of the formula (II) according to the reaction scheme below:

-   (d) reaction of aminophenols of the formula (XII) with 4-substituted    phenyl derivatives of the formula (IV) according to the reaction    scheme below:

-   (e) reduction of the nitrophenyl ethers of the formula (VI) to    aniline ethers of the formula (VIII) according to the reaction    scheme below:

-   (f) reaction of the aniline ethers of the formula (VIII) with    -   (i) aminoacetals of the formula (XIII) or    -   (ii) with amides of the formula (XIV) or    -   (iii) with amines of the formula (XV) in the presence of ortho        esters of the formula (XVI) according to the reaction scheme        below:

-   (g) reaction of the aminophenols of the formula (XII) with    -   (i) aminoacetals of the formula (XIII) or    -   (ii) with amides of the formula (XIV) or    -   (iii) with amines of the formula (XV) in the presence of ortho        esters of the formula (XVI) according to the reaction scheme        below:

-   (h) reaction of the aminophenols of the formula (VII) with    -   (i) aminoacetals of the formula (XIII) or    -   (ii) with amides of the formula (XIV) or    -   (iii) with amines of the formula (XV) in the presence of ortho        esters of the formula (XVI) according to the reaction scheme        below:

-   (i) reaction of amidines of the formula (XI) with 4-substituted    phenols of the formula (II) according to the reaction scheme below:

-   (j) reaction of amidines of the formula (XI) with 4-substituted    phenyl derivatives of the formula (IV) according to the reaction    scheme below:

where in the formulae mentioned above

-   R¹ to R⁷ have the above meanings;-   R⁸ and R⁹ independently of one another are selected from the group    consisting of hydrogen, C₁₋₁₂-alkyl, C₂₋₁₂-alkenyl, C₂₋₁₂-alkynyl or    C₅₋₁₈-aryl or C₇₋₁₉-arylalkyl groups and which together with the    oxygen atoms to which they are attached may form a five-, six- or    seven-membered ring;-   R¹⁰ to R¹² independently of one another are selected from the group    consisting of hydrogen, C₁₋₁₂-alkyl, C₂₋₁₂-alkenyl, C₂₋₁₂-alkynyl or    C₅₋₁₈-aryl or C₇₋₁₉-arylalkyl, C₇₋₁₉-alkylaryl groups and in each    case R¹⁰ with R¹², R¹⁰ with R¹¹ or R¹¹ with R¹² together with the    oxygen atoms to which they are attached and if appropriate with    further carbon, nitrogen, oxygen, phosphorus or sulfur atoms may    form a five-, six- or seven-membered ring.

A third subject matter of the invention relates to 4-cycloalkyl- or4-aryl-substituted nitrophenyl ethers of the formula (VI)

in which R⁴ to R⁷ have the above meanings.

A fourth subject matter of the invention relates to 4-cycloalkyl- or4-aryl-substituted aniline ethers of the formula (VIII)

in which R⁴ to R⁷ have the above meanings.

A fifth subject matter of the invention is the use of the 4-cycloalkyl-or 4-aryl-substituted phenoxyphenylamidines according to the inventionor Error! Reference source not found. A sixth subject matter of thepresent invention is a composition for controlling unwantedmicroorganisms, comprising at least one 4-cycloalkyl- or4-aryl-substituted phenoxyphenylamidine according to the presentinvention.

A further subject matter of the invention relates to a method forcontrolling unwanted microorganisms, characterized in that thephenoxyphenylamidines according to the invention are applied to themicroorganisms and/or their habitat.

Moreover, the invention relates to seed which has been treated with atleast one of the amidines according to the invention.

A final subject matter of the invention relates to a method forprotecting seed against unwanted microorganisms by using seed treatedwith at least one phenoxyphenylamidine of the present invention.

General Definitions

In connection with the present invention, the term halogens (X)comprises, unless otherwise defined, those elements which are chosenfrom the group consisting of fluorine, chlorine, bromine and iodine,where fluorine, chlorine and bromine are preferably used and fluorineand chlorine are particularly preferably used.

Optionally substituted groups can be mono- or polysubstituted, where inthe case of polysubstitution the substituents can be identical ordifferent.

In connection with the present invention, the group —X denotes a halogenatom selected from the group consisting of fluorine, chlorine, bromineand iodine, preferably fluorine, chlorine and bromine, particularlypreferably from the group consisting of fluorine and chlorine.

Alkyl groups substituted by one or more halogen atoms (—X) are, forexample, selected from the group consisting of trifluoromethyl (CF₃),difluoromethyl (CHF₂), CF₃CH₂, ClCH₂, CF₃CCl₂.

In connection with the present invention, alkyl groups are, unlessotherwise defined, straight-chain, branched or cyclic hydrocarbon groupswhich may optionally have one, two or more single or doubleunsaturations or one, two or more heteroatoms selected from the groupconsisting of O, N, P and S. Moreover, the alkyl groups according to theinvention may optionally be substituted be further groups selected fromthe group consisting of —R′, halogen (—X), alkoxy (—OR′), thioether ormercapto (—SR′), amino (—NR′₂), silyl (—SiR′₃), carboxyl (—COOR′), cyano(—CN), acyl (—(C═O)R′) and amide groups (—CONR′₂), where R′ representshydrogen or a C₁₋₁₂-alkyl group, preferably a C₂₋₁₀-alkyl group,particularly preferably a C₃₋₈-alkyl group which may have one or moreheteroatoms selected from the group consisting of N, O, P and S.

The definition C₁-C₁₂-alkyl comprises the biggest range defined hereinfor an alkyl group. Specifically, this definition comprises, forexample, the meanings methyl, ethyl, n-, isopropyl, n-, iso-, sec- andt-butyl, n-pentyl, n-hexyl, 1,3-dimethylbutyl, 3,3-dimethylbutyl,n-heptyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl.

In connection with the present invention, alkenyl groups are, unlessotherwise defined, straight-chain, branched or cyclic hydrocarbon groupswhich comprise at least one single unsaturation (double bond) and mayoptionally have one, two or more single or double unsaturations or one,two or more heteroatoms selected from the group consisting of O, N, Pand S. Moreover, the alkenyl groups according to the invention mayoptionally be substituted by further groups selected from the groupconsisting of —R′, halogen (—X), alkoxy (—OR′), thioether or mercapto(—SR′), amino (—NR′₂), silyl (—SiR′₃), carboxyl (—COOR′), cyano (—CN),acyl (—(C═O)R′) and amide groups (—CONR′₂), where R′ represents hydrogenor a C₁₋₁₂-alkyl group, preferably C₂₋₁₀-alkyl group, particularlypreferably C₃₋₈-alkyl group, which may have one or more heteroatomsselected from the group consisting of N, O, P and S.

The definition C₂-C₁₂-alkenyl comprises the biggest range defined hereinfor an alkenyl group. Specifically, this definition comprises, forexample, the meanings vinyl; allyl (2-propenyl), isopropenyl(1-methylethenyl); but-1-enyl (crotyl), but-2-enyl, but-3-enyl;hex-1-enyl, hex-2-enyl, hex-3-enyl, hex-4-enyl, hex-5-enyl; hept-1-enyl,hept-2-enyl, hept-3-enyl, hept-4-enyl, hept-5-enyl, hept-6-enyl;oct-1-enyl, oct-2-enyl, oct-3-enyl, oct-4-enyl, oct-5-enyl, oct-6-enyl,oct-7-enyl; non-1-enyl, non-2-enyl, non-3-enyl, non-4-enyl, non-5-enyl,non-6-enyl, non-7-enyl, non-8-enyl; dec-1-enyl, dec-2-enyl, dec-3-enyl,dec-4-enyl, dec-5-enyl, dec-6-enyl, dec-7-enyl, dec-8-enyl, dec-9-enyl;undec-1-enyl, undec-2-enyl, undec-3-enyl, undec-4-enyl, undec-5-enyl,undec-6-enyl, undec-7-enyl, undec-8-enyl, undec-9-enyl, undec-10-enyl;dodec-1-enyl, dodec-2-enyl, dodec-3-enyl, dodec-4-enyl, dodec-5-enyl,dodec-6-enyl, dodec-7-enyl, dodec-8-enyl, dodec-9-enyl, dodec-10-enyl,dodec-11-enyl; buta-1,3-dienyl, penta-1,3-dienyl.

In connection with the present invention, alkynyl groups are, unlessotherwise defined, straight-chain, branched or cyclic hydrocarbon groupswhich comprise at least one double unsaturation (triple bond) and mayoptionally have one, two or more single or double unsaturations or one,two or more heteroatoms selected from the group consisting of O, N, Pand S. Moreover, the alkynyl groups according to the invention mayoptionally be substituted by further groups selected from the groupconsisting of —R′, halogen (—X), alkoxy (—OR′), thioether or mercapto(—SR′), amino (—NR′₂), silyl (—SiR′₃), carboxyl (—COOR′), cyano (—CN),acyl-(—(C═O)R′) and amide groups (—CONR′₂), where R′ represents hydrogenor a straight-chain, branched or cyclic C₁₋₁₂-alkyl group which may haveone or more heteroatoms selected from the group consisting of N, O, Pand S.

The definition C₂-C₁₂-alkynyl comprises the biggest range defined hereinfor an alkynyl group. Specifically, this definition comprises, forexample, the meanings ethynyl (acetylenyl), prop-1-ynyl and prop-2-ynyl.

In connection with the present invention, aryl groups are, unlessotherwise defined, aromatic hydrocarbon groups which may have one, twoor more heteroatoms selected from the group consisting of O, N, P and Sand may optionally be substituted by further groups selected from thegroup consisting of —R′, halogen (—X), alkoxy (—OR′), thioether ormercapto (—SR′), amino (—NR′₂), silyl (—SiR′₃), carboxyl (—COOR′), cyano(—CN), acyl (—(C═O)R′) and amide groups (—CONR′₂), where R′ representshydrogen or a C₁₋₁₂-alkyl group, preferably C₂₋₁₀-alkyl group,particularly preferably C₃₋₈-alkyl group, which may have one or moreheteroatoms selected from the group consisting of N, O, P and S.

The definition C₅₋₁₈-aryl comprises the biggest range defined herein foran aryl group having 5 to 18 atoms. Specifically, this definitioncomprises, for example, the meanings cyclopentadienyl, phenyl,cyclo-heptatrienyl, cyclooctatetraenyl, naphthyl and anthracenyl.

In connection with the present invention, arylalkyl groups (aralkylgroups) are, unless otherwise defined, alkyl groups substituted by arylgroups which may have a C₁₋₈-alkylene chain and may be substituted inthe aryl skeleton or in the alkylene chain by one or more heteroatomsselected from the group consisting of O, N, P and S and optionally byfurther groups selected from the group consisting of —R′, halogen (—X),alkoxy (—OR′), thioether or mercapto (—SR′), amino (—NR′₂), silyl(—SiR′₃), carboxyl (—COOR′), cyano (—CN), acyl (—(C═O)R′) and amidegroups (—CONR′₂), where R′ represents hydrogen or a C₁₋₁₂-alkyl group,preferably C₂₋₁₀-alkyl group, particularly preferably C₃₋₈-alkyl group,which may have one or more heteroatoms selected from the groupconsisting of N, O, P and S.

The definition C₇₋₁₉-aralkyl group comprises the biggest range definedherein for an aralkyl group having a total of 7 to 19 atoms in theskeleton and the alkylene chain. Specifically, this definitioncomprises, for example, the meanings benzyl and phenylethyl.

In connection with the present invention, alkylaryl groups (alkarylgroups) are, unless otherwise defined, aryl groups substituted by alkylgroups which may have a C₁₋₈-alkylene chain and may be substituted inthe aryl skeleton or the alkylene chain by one or more heteroatomsselected from the group consisting of O, N, P and S and optionally byfurther groups selected from the group consisting of —R′, halogen (—X),alkoxy (—OR′), thioether or mercapto (—SR′), amino (—NR′₂), silyl(—SiR′₃), carboxyl (—COOR′), cyano (—CN), acyl (—(C═O)R′) and amidegroups (—CONR′₂), where R′ represents hydrogen or a C₁₋₁₂-alkyl group,preferably C₂₋₁₀-alkyl group, particularly preferably C₃₋₈-alkyl group,which may have one or more heteroatoms selected from the groupconsisting of N, O, P and S.

The definition C₇₋₁₉-alkylaryl group comprises the biggest range definedherein for an alkylaryl group having a total of 7 to 19 atoms in theskeleton and the alkylene chain. Specifically, this definitioncomprises, for example, the meanings tolyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-or 3,5-dimethylphenyl.

The alkyl, alkenyl, alkynyl, aryl, alkaryl and aralkyl groups mayfurthermore have one or more heteroatoms which—unless otherwisedefined—are chosen from the group consisting of N, O, P and S. Here, theheteroatoms replace the carbon atoms indicated.

The compounds according to the invention may, if appropriate, exist asmixtures of different possible isomeric forms, in particularstereoisomers, such as, for example, E- and Z-, threo- and erythro-, andalso optical isomers, but, if appropriate, also tautomers. What isdisclosed and claimed are both the E- and the Z-isomers, and also thethreo- and erythro-, and also the optical isomers, any mixtures of theseisomers, and also the possible tautomeric forms.

The 4-cycloalkyl- or 4-aryl-substituted amidines according to theinvention are compounds of the formula (I)

or their salts, N-oxides, metal complexes and their stereoisomers.

In the formula (I), the groups have the meanings defined below. Thegiven definitions also apply to all intermediates:

-   R¹ is selected from the group consisting of:    -   hydrogen;    -   straight-chain, branched C₁₋₁₂-alkyl, C₂₋₁₂-alkenyl,        C₂₋₁₂₋alkynyl groups or cyclic C₃₋₈-alkyl, C₄₋₈-alkenyl,        C₄₋₈-alkynyl groups, where in the ring system of all of the        cyclic groups mentioned above one or more carbon atoms may be        replaced by heteroatoms selected from the group consisting of N,        O, P and S and all of the groups mentioned above may be        substituted by one or more groups selected from the group        consisting of —R′, halogen (—X), alkoxy (—OR′), thioether or        mercapto (—SR′), amino (—NR′₂), silyl (—SiR′₃), carboxyl        (—COOR′), cyano (—CN) and amide groups (—CONR′₂), where R′ may        represent hydrogen or a C₁₋₁₂-alkyl group, preferably        C₂₋₁₀-alkyl group, particularly preferably C₃₋₈-alkyl group,    -   mercapto (—SH) and thioether groups (—SR″), where R″ represents        a C₁₋₁₂-alkyl group, preferably C₂₋₁₀-alkyl group, particularly        preferably C₃₋₈-alkyl group, where in the ring system of all of        the cyclic groups mentioned above one or more carbon atoms may        be replaced by heteroatoms selected from the group consisting of        N, O, P and S and all of the groups mentioned above may be        substituted by groups, where the groups mentioned above are        selected from the group consisting of —R′, halogen (—X), alkoxy        (—OR′), thioether or mercapto (—SR′), amino (—NR′₂), silyl        (—SiR′₃), carboxyl (—COOR′), cyano (—CN) and amide groups        (—CONR′₂), where R′ has the above meanings.-   R² is selected from the group consisting of:    -   straight-chain, branched C₁₋₁₂-alkyl, C₂₋₁₂-alkenyl,        C₂₋₁₂-alkynyl groups, cyclic C₃₋₈-alkyl, C₄₋₈-alkenyl,        C₄₋₈-alkynyl groups or C₅₋₁₈-aryl, C₇₋₁₉-aralkyl or        C₇₋₁₉-alkaryl groups, where in the ring system of all of the        cyclic groups mentioned above one or more carbon atoms may be        replaced by heteroatoms selected from the group consisting of N,        O, P and S and all of the groups mentioned above may be        substituted by one or more groups selected from the group        consisting of —R′, halogen (—X), alkoxy (—OR′), thioether or        mercapto (—SR′), amino (—NR′₂), silyl (—SiR′₃), carboxyl        (—COOR′), cyano (—CN) and amide groups (—CONR′₂), where R′ has        the above meanings.-   R³ is selected from the group consisting of:    -   cyano (—CN), mercapto (—SH), thioether (—SR″), alkoxy (—OR″) and        acyl groups (—(C═O)—R″), where R′ has the above meanings;    -   straight-chain, branched C₁₋₁₂-alkyl, C₂₋₁₂-alkenyl,        C₂₋₁₂-alkynyl groups, cyclic C₃₋₈-alkyl, C₄₋₈-alkenyl,        C₄₋₈-alkynyl groups or C₅₋₁₈-aryl or C₇₋₁₉-aralkyl groups, where        in the ring system of all of the cyclic groups mentioned above        one or more carbon atoms may be replaced by heteroatoms selected        from the group consisting of N, O, P and S and all of the groups        mentioned above may be substituted by one or more groups        selected from the group consisting of —R′, halogen (—X), alkoxy        (—OR′), thioether or mercapto (—SR′), amino (—NR′₂), silyl        (—SiR′₃), carboxyl (—COOR′), cyano (—CN) and amide groups        (—CONR′₂), where R′ has the above meanings.

In an alternative embodiment of the invention, R² and R³, R² and R¹ or

-   R¹ and R³ together with the atoms to which they are attached or with    further atoms selected from the group consisting of N, O, P and S    may form a four- to seven-membered, preferably a five- to    six-membered ring which may be substituted by R′, halogen (—X),    alkoxy (—OR′), thioether or mercapto (—SR′), amino (—NR′₂), silyl    (—SiR′₃), carboxyl (—COOR′), cyano (—CN) and amide groups (—CONR′₂)    where R′ has the above meanings.-   R⁴ is selected from the group consisting of:    -   halogen atoms (X—);    -   cyano (—CN), mercapto (—SH), thioether (—SR″), alkoxy (—OR″) and        acyl groups (—(C═O)—R″), where has the above meanings;    -   straight-chain, branched C₁₋₁₂-alkyl, C₂₋₁₂-alkenyl,        C₂₋₁₂-alkynyl groups, cyclic C₃₋₈-alkyl, C₄₋₈-alkenyl,        C₄₋₈-alkynyl groups or C₅₋₁₈-aryl, C₇₋₁₉-aralkyl or        C₇₋₁₉-alkaryl groups, where in the ring system of all of the        cyclic groups mentioned above one or more carbon atoms may be        replaced by heteroatoms selected from the group consisting of N,        O, P and S and all of the groups mentioned above may be        substituted by one or more groups selected from the group        consisting of —R′, halogen (—X), alkoxy (—OR′), thioether or        mercapto (—SR′), amino (—NR′₂), silyl (—SiR′₃), carboxyl        (—COOR′), cyano (—CN) and amide groups (—CONR′₂), where R′ has        the above meanings.-   R⁵ is selected from the group consisting of:    -   hydrogen;    -   halogen atoms (X—);    -   cyano (—CN), mercapto (—SH), thioether (—SR″), alkoxy (—OR″) and        acyl groups (—(C═O)—R″), where R″ has the above meanings;    -   straight-chain, branched C₁₋₁₂-alkyl, C₂₋₁₂-alkenyl,        C₂₋₁₂-alkynyl groups, cyclic C₃₋₈-alkyl, C₄₋₈-alkenyl,        C₄₋₈-alkynyl groups or C₅₋₁₈-aryl, C₇₋₁₉-aralkyl or        C₇₋₁₉-alkaryl groups, where in the ring system of all of the        cyclic groups mentioned above one or more carbon atoms may be        replaced by heteroatoms selected from the group consisting of N,        O, P and S and all of the groups mentioned above may be        substituted by one or more groups selected from the group        consisting of —R′, halogen (—X), alkoxy (—OR′), thioether or        mercapto (—SR′), amino (—NR′₂), silyl (—SiR′₃), carboxyl        (—COOR′), cyano (—CN) and amide groups (—CONR′₂), where R′ has        the above meanings.-   R⁶ is selected from the group consisting of hydrogen, halogen atoms    and C₁₋₆-haloalkyl groups;-   R⁷ is selected from the group consisting of alicyclic C₃₋₁₂-alkyl,    C₄₋₁₂-alkenyl, C₄₋₁₂-alkynyl groups or C₅₋₁₈-aryl, C₇₋₁₉-aralkyl or    C₇₋₁₉-alkaryl groups, which may be substituted by one or more groups    selected from the group consisting of —R′, —X, —OR′, —SO₂—R′, —SR′,    —NR′₂, —SiR′₃, —COOR′, —CN and —CONR′₂, where R′ has the above    meanings and where the C₅₋₁₈-aryl, C₇₋₁₉-aralkyl and C₇₋₁₉-alkaryl    groups may be substituted by one or more heteroatoms selected from    the group consisting of N, O, P and S.

In formula (I), the groups have the preferred meanings defined below.The definitions given as being preferred likewise apply to allintermediates:

-   R¹ is preferably selected from the group consisting of hydrogen, a    mercapto group (—SH) or C₁₋₈-alkyl group.-   R² is preferably selected from the group consisting of    straight-chain or branched, C₁₋₈-alkyl groups.-   R³ is preferably selected from the group consisting of    straight-chain, branched and alicyclic C₂₋₈-alkyl groups.

In an alternative preferred embodiment of the invention, R² and R³together with the nitrogen atom to which they are attached or withfurther atoms, selected from the group consisting of N and O, maypreferably form a five- or six-membered ring.

-   R⁴ is preferably selected from the group consisting of —X,    straight-chain or branched, C₁₋₈-alkyl groups and C₁₋₅-haloalkyl    groups.-   R⁵ is preferably selected from the group consisting of —X,    straight-chain or branched, C₁₋₈-alkyl groups and C₁₋₅-haloalkyl    groups.-   R⁶ is preferably selected from the group consisting of hydrogen,    fluorine, chlorine, bromine, —CF₃, —CHF₂.-   R⁷ is preferably selected from phenyl, cyclopropyl, cyclobutyl,    cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl groups which may be    substituted by one or more groups selected from the group consisting    of —R′, —X, —OR′, —SR′, —SO₂—R′, —NR′₂, —SiR′₃, —COOR′, —CN and    —CONR′₂, where R′ has the above meanings.

In the formula (I), the groups have the particularly preferred meaningsdefined below. The definitions given as being particularly preferredlikewise apply to all intermediates:

-   R′ is particularly preferably selected from the group consisting of    hydrogen, methyl and ethyl.-   R² is particularly preferably selected from the group consisting of    methyl and ethyl.-   R³ is particularly preferably selected from the group consisting of    ethyl and cyclopropyl.

Alternatively to this, R² and R³ may particularly preferably form apiperidyl or pyrrolidyl ring with each other.

-   R⁴ is particularly preferably selected from Cl and F atoms and —CF₃,    —CF₂H and methyl groups.-   R⁵ is independently of R⁴ particularly preferably selected from Cl    and F atoms and —CF₃, —CF₂H and methyl groups.-   R⁶ is particularly preferably selected from the group consisting of    hydrogen, methyl and ethyl.-   R⁷ is particularly preferably selected from the group consisting of    phenyl, 4-chlorophenyl, 4-ethylsulfonylphenyl,    4-trifluoromethylphenyl, 4-dimethylaminophenyl, 4-methoxyphenyl,    4-tert-butylphenyl, 4-acetylphenyl, 4-fluorophenyl, 2-ethylphenyl,    2-trifluoromethylphenyl, 2-isopropylphenyl, 2-methylphenyl,    2-fluorophenyl, 2-acetylphenyl, 2-methoxyphenyl, 2-chlorophenyl,    2-(2-methylpropoxy)phenyl, cyclopropyl, cyclohexyl, cycloheptyl,    cyclooctyl.

Depending on the nature of the substituents defined above, the amidinesaccording to the invention have acidic or basic properties and can formsalts, if appropriate also internal salts or adducts, with inorganic ororganic acids or with bases or with metal ions.

Suitable metal ions are in particular the ions of the elements of thesecond main group, in particular calcium and magnesium, of the third andfourth main group, in particular aluminum, tin and lead, and of thefirst to eighth subgroups, in particular chromium, manganese, iron,cobalt, nickel, copper, zinc and others. Particular preference is givento the metal ions of the elements of the fourth period. Here, the metalscan be present in the various valencies that they can assume.

If the compounds of the formula (I) carry hydroxyl groups, carboxylgroups or other groups inducing acidic properties, these compounds canbe reacted with bases to give salts.

Suitable bases are, for example, hydroxides, carbonates, bicarbonates ofthe alkali metals and alkaline earth metals, in particular those ofsodium, potassium, magnesium and calcium, furthermore ammonia, primary,secondary and tertiary amines having (C₁-C₄)-alkyl groups, mono-, di-and trialkanolamines of (C₁-C₄)-alkanols, choline and alsochlorocholine.

If the compounds of the formula (I) carry amino groups, alkylaminogroups or other groups which induce basic properties, these compoundscan be reacted with acids to give salts.

Examples of inorganic acids are hydrohalic acids, such as hydrogenfluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide,sulfuric acid, phosphoric acid and nitric acid, and acidic salts, suchas NaHSO₄ and KHSO₄.

Suitable organic acids are, for example, formic acid, carbonic acid andalkanoic acids, such as acetic acid, trifluoroacetic acid,trichloroacetic acid and propionic acid, and also glycolic acid,thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid,cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids havingstraight-chain or branched alkyl groups having 1 to 20 carbon atoms),arylsulfonic acids or -disulfonic acids (aromatic groups, such as phenyland naphthyl, which carry one or two sulfonic acid groups),alkylphosphonic acids (phosphonic acids having straight-chain orbranched alkyl groups having 1 to 20 carbon atoms), arylphosphonic acidsor -diphosphonic acids (aromatic groups, such as phenyl and naphthyl,which carry one or two phosphonic acid groups), where the alkyl and arylgroups may carry further substituents, for example p-toluenesulfonicacid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid,2-acetoxybenzoic acid, etc.

The salts obtainable in this manner also have fungicidal properties.

Amidines particularly preferred in connection with the present inventionare selected from the group consisting ofN′-{4-[(4′-chlorobiphenyl-4-yl)oxy]-2,5-dimethylphenyl}-N-ethyl-N-methylimidoformamide(1),N-ethyl-N′-(4-{[4′-(ethylsulfonyl)biphenyl-4-yl]oxy}-2,5-dimethylphenyl)-N-methylimidoformamide(2),N′-(2,5-dimethyl-4-{[4′-(trifluoromethyl)biphenyl-4-yl]oxy}phenyl)-N-ethyl-N-methylimidoformamide(3),N′-(4-{[4′-(dimethylamino)biphenyl-4-yl]oxy}-2,5-dimethylphenyl)-N-ethyl-N-methylimidoformamide(4),N-ethyl-N′-{4-[(4′-methoxybiphenyl-4-yl)oxy]-2,5-dimethylphenyl}-N-methylimidoformamide(5),N′-(2,5-dimethyl-4-{[4′-(methylthio)biphenyl-4-yl]oxy}phenyl)-N-ethyl-N-methylimidoformamide(6),N′-(2,5-dimethyl-4-{[4′-(tert-butyl)biphenyl-4-yl]oxy}phenyl)-N-ethyl-N-methylimidoformamide(7),N′-{4-[(4′-acetylbiphenyl-4-yl)oxy]-2,5-dimethylphenyl}-N-ethyl-N-methylimidoformamide(8),N′-[4-({4′-[(E)-(butoxyimino)methyl]biphenyl-4-yl}methyl)-2,5-dimethylphenyl]-N-ethyl-N-methylimidoformamide(10),N-ethyl-N′-{4-[(4′-fluorobiphenyl-4-yl)methyl]-2,5-dimethylphenyl}-N-methylimidoformamide(11),N-ethyl-N′-[4-({4′-[(E)-(methoxyimino)methyl]biphenyl-4-yl}methyl)-2,5-dimethylphenyl]-N-methylimidoformamide(12),N-ethyl-N′-{4-[(2′-ethylbiphenyl-4-yl)methyl]-2,5-dimethylphenyl}-N-methylimidoformamide(13)N′-(2,5-dimethyl-4-{[2′-(trifluoromethyl)biphenyl-4-yl]methyl}phenyl)-N-ethyl-N-methyl-imidoformamide(14),N-ethyl-N′-{4-[(2′-isopropylbiphenyl-4-yl)methyl]-2,5-dimethylphenyl}-N-methylimidoformamide(15),N-ethyl-N′-{4-[(2′-methylbiphenyl-4-yl)methyl]-2,5-dimethylphenyl}-N-methylimidoformamide(16),N-ethyl-N′-{4-[(2′-fluorobiphenyl-4-yl)methyl]-2,5-dimethylphenyl}-N-methylimidoformamide(17),N′-{4-[(2′-acetylbiphenyl-4-yl)methyl]-2,5-dimethylphenyl}-N-ethyl-N-methylimidoformamide(18),N′-{4-[(2′-methoxybiphenyl-4-yl)methyl]-2,5-dimethylphenyl}-N-ethyl-N-methylimidoformamide(19),2,5-dimethyl-N-[(1E)-piperidin-1-ylmethylene]-4-{[2′-(trifluoromethyl)biphenyl-4-yl]methyl}aniline(20),2,5-dimethyl-N-[(1E)-piperidin-1-ylmethylene]-4-{[2′-fluorobiphenyl-4-yl]methyl}aniline(21),2,5-dimethyl-N-[(1E)-piperidin-1-ylmethylene]-4-{[2′-acetylbiphenyl-4-yl]methyl}aniline(22),2,5-dimethyl-N-[(1E)-piperidin-1-ylmethylene]-4-{[2′-ethylbiphenyl-4-yl]methyl}aniline(23),2,5-dimethyl-N-[(1E)-piperidin-1-ylmethylene]-4-{[2′-methylbiphenyl-4-yl]methyl}aniline(24),2,5-dimethyl-N-[(1E)-piperidin-1-ylmethylene]-4-{[2′-isopropylbiphenyl-4-yl]methyl}aniline(25),2,5-dimethyl-N-[(1E)-piperidin-1-ylmethylene]-4-{[2′-chlorobiphenyl-4-yl]methyl}aniline(26),N′-{4-[(2′-chlorobiphenyl-4-yl)oxy]-2,5-dimethylphenyl}-N-ethyl-N-methylimidoformamide(27),4-[(2′-isobutoxybiphenyl-4-yl)oxy]-2,5-dimethyl-N-[(1E)-piperidin-1-ylmethylene]aniline(28),N-ethyl-N′-{4-[(2′-isobutoxybiphenyl-4-yl)oxy]-2,5-dimethylphenyl}-N-methylimidoformamide(29),4-[(4′-fluorobiphenyl-4-yl)oxy]-2,5-dimethyl-N-[(1E)-pyrrolidin-1-ylmethylene]aniline(30),N′-[4-(biphenyl-4-yloxy)-2,5-dimethylphenyl]-N-ethyl-N-methylimidoformamide(31),N′-[4-(4-cyclopentylphenoxy)-2,5-dimethylphenyl]-N-ethyl-N-methylimidoformamide(32),N′-[4-(4-cyclopentylphenoxy)-2,5-dimethylphenyl]-N-isopropyl-N-methylimidoformamide(33),4-(4-cyclopentylphenoxy)-2,5-dimethyl-N-[(1E)-(2-methylpiperidin-1-yl)methylene]aniline(34),4-(4-cyclopentylphenoxy)-2,5-dimethyl-N-[(1E)-piperidin-1-ylmethylene]aniline(35),N′-[4-(2-chloro-4-cyclopentylphenoxy)-2,5-dimethylphenyl]-N-ethyl-N-methylimidoformamide(36),N′-{4-[4-cyclopentyl-2-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl}-N-ethyl-N-methylimidoformamide(37),N′-{4-[4-cyclohexylphenoxy]-2,5-dimethylphenyl}-N-ethyl-N-methylimidoformamide(38),N′-{4-[4-cyclohexyl-phenoxy]-2,5-dimethylphenyl}-N-isopropyl-N-methylimidoformamide(39),N′-{4-[4-cyclohexyl-2-phenoxy]-2,5-dimethylphenyl}-N-[(1E)-(2-methylpiperidin-1-yl)methylene]aniline(40),4-(4-cyclohexylphenoxy)-2,5-dimethyl-N-[(1E)-piperidin-1-ylmethylene]aniline(41) andN′-{4-[4-cyclohexyl-2-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl}-N-ethyl-N-methylimidoformamide(42).

Preparation of the Amidines According to the Invention

The amidines according to the invention can be obtained by the processshown in scheme (I) below:

Step (a)

In one embodiment according to the invention, nitrobenzene derivativesof the formula (III) are reacted with 4-substituted phenols of theformula (II) or the phenoxides formed therefrom in accordance with thereaction scheme below to give nitrophenyl ethers of the formula (VI):

Suitable leaving groups (Z) are all substituents having sufficientnucleofugicity under the prevailing reaction conditions. Examples ofsuitable leaving groups to be mentioned are halogens, triflate,mesylate, tosylate or SO₂Me.

The reaction is carried out in the presence of a base, if appropriate.

Suitable bases are organic and inorganic bases which are usually used insuch reactions. Preference is given to using bases which, for example,are selected from the group consisting of hydrides, hydroxides, amides,alkoxides, acetates, fluorides, phosphates, carbonates and bicarbonatesof alkali metals or alkaline earth metals. Particular preference isgiven here to sodium amide, sodium hydride, lithium diisopropylamide,sodium methoxide, potassium tert-butoxide, sodium hydroxide, potassiumhydroxide, sodium acetate, sodium phosphate, potassium phosphate,potassium fluoride, cesium fluoride, sodium carbonate, potassiumcarbonate, potassium bicarbonate, sodium bicarbonate and cesiumcarbonate. Furthermore, tertiary amines, such as, for example,trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline,N,N-dimethylbenzylamine, pyridine, N-methylpiperidine,N-methylpyrolidone, N,N-dimethylaminopyridine, diazabicyclooctane(DABCO), diazabicyclononene (DBN) and diazabicycloundecene (DBU).

If appropriate, a catalyst chosen from the group consisting ofpalladium, copper and their salts or complexes may be used.

The reaction of the nitrobenzene derivative with the phenol can becarried out neat or in a solvent; preferably, the reaction is carriedout in a solvent selected from standard solvents which are inert underthe prevailing reaction conditions.

Preference is given to aliphatic, alicyclic or aromatic hydrocarbons,such as, for example, petroleum ether, hexane, heptane, cyclohexane,methylcyclohexane, benzene, toluene, xylene or decalin; halogenatedhydrocarbons, such as, for example, chlorobenzene, dichlorobenzene,dichloromethane, chloroform, carbon tetrachloride, dichloroethane ortrichloroethane; ethers, such as, for example, diethyl ether,diisopropyl ether, methyl tert-butyl ether (MTBE), methyl tert-amylether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethaneor anisole; nitriles, such as, for example, acetonitrile, propionitrile,n- or isobutyronitrile or benzonitrile; amides, such as, for example,N,N-dimethylformamide (DMF), N,N-dimethylacetamide, N-methylformanilide,N-methylpyrrolidone (NMP) or hexamethylenephosphoric triamide; ormixtures of these with water, and also pure water.

The reaction can be carried out under reduced pressure, at atmosphericpressure or under superatmospheric pressure and at temperatures of from−20 to 200° C.; preferably, the reaction is carried out at atmosphericpressure and temperatures of from 50 to 150° C.

Step (b)

In an alternative embodiment according to the invention, nitrophenolderivatives of the formula (V) or the phenoxides formed therefrom arereacted with 4-substituted phenyl derivatives of the formula (IV) inaccordance with the reaction scheme below to give nitrophenyl ethers ofthe formula (VI):

With regard to the reaction conditions, the solvents, the catalysts andthe suitable leaving groups, reference may be made to step (a).

Step (c)

In a further alternative embodiment according to the invention, anilinesof the formula (VII) are reacted with 4-substituted phenols of theformula (II) or the phenoxides formed therefrom in accordance with thereaction scheme below to give aminophenyl ethers of the formula (VIII):

With regard to the reaction conditions, the solvents, the catalysts andthe suitable leaving groups, reference may be made to step (a).

Step (d)

In a further alternative embodiment according to the invention,aminophenols of the formula (XII) are reacted with 4-substituted phenylderivatives of the formula (IV) in accordance with the reaction schemebelow to give aminophenyl ethers of the formula (VIII):

With regard to the reaction conditions, the solvents, the catalysts andthe suitable leaving groups, reference may be made to step (c).

Step (e)

The nitrophenyl ethers of the formula (VI) obtained in steps (a) and (b)can be reduced in accordance with the reaction scheme below to give theaniline ethers of the formula (VIII):

The reduction according to step (e) can be carried out by any methodsfor reducing nitro groups described in the prior art.

If appropriate, the reduction is carried out using tin chloride inconcentrated hydrochloric acid, as described in WO 0046184. However,alternatively, the reduction can also be carried out by using hydrogengas, preferably in the presence of suitable hydrogenation catalysts,such as, for example, Raney nickel, Pd/C. The reaction conditions havealready been described in the prior art and are familiar to the personskilled in the art.

If the reduction is carried out in the liquid phase, the reaction shouldtake place in a solvent inert to the prevailing reaction conditions. Onesuch solvent is, for example, toluene.

Step (f)

The conversion of the aniline ethers of the formula (VIII) into theamidines of the formula (I) according to the invention according to step(f) can be carried out, as shown above in schema (I), using differentalternative methods employing

-   (i) aminoacetals of the formula (XIII) or-   (ii) amides of the formula (XIV) or-   (iii) amines of the formula (XV) in the presence of ortho esters of    the formula (XVI)    according to the reaction scheme below:

The individual alternative embodiments (i) to (iii) of the processaccording to the invention are briefly illustrated below:

-   (i) According to one embodiment according to the invention, shown in    scheme (I) as step (i), the aniline ethers of the formula (VIII) are    reacted with aminoacetals of the formula (XIII) in which R² and R³    are defined as described above and R⁸ and R⁹ are selected from the    group consisting of C₁₋₈-alkyl groups, preferably from C₂₋₆-alkyl    groups, particularly preferably from C₃₋₅-alkyl groups, and which    together with the oxygen atoms to which they are attached may form a    five- or six-membered carbocyclic ring, to give the    phenoxyphenylamidines of the formula (I) according to the invention.    -   The aminoacetals of the formula (XIII) can be obtained from the        formamides described in JACS, 65, 1566 (1943), by reaction with        alkylating agents, such as, for example, dimethyl sulfate.    -   The reaction according to step (i) is carried out in the        presence of an acid, if appropriate.    -   Suitable acids are, for example, selected from the group        consisting of organic and inorganic acids, and p-toluenesulfonic        acid, methanesulfonic acid, hydrochloric acid (gaseous, aqueous        or in organic solution) or sulfuric acid.-   (ii) In an alternative embodiment according to the invention, shown    in scheme (I) as step (ii), the aniline ethers of the formula (VIII)    are reacted with amides of the formula (XIV) in which the groups R¹    to R³ are as defined above to give the phenoxyphenylamidines    according to the invention.    -   The reaction according to step (ii) is, if appropriate, carried        out in the presence of a halogenating agent. Suitable        halogenating agents are, for example, selected from the group        consisting of PCl₅, PCl₃, POCl₃ or SOCl₂.    -   Moreover, the reaction may alternatively be carried out in the        presence of a condensing agent.    -   Suitable condensing agents are those usually employed for        forming amide bonds; acid halide formers, such as, for example,        phosgene, phosphorus tribromide, phosphorus trichloride,        phosphorus pentachloride, phosphorus oxytrichloride or thionyl        chloride; anhydride formers, such as, for example,        chloroformate, methyl chloroformate, isopropyl chloroformate,        isobutyl chloroformate or methanesulfonyl chloride;        carbodiimines, such as, for example,        N,N′-dicyclohexylcarbodiimine (DCC) or other customary        condensing agents, such as, for example, phosphorus pentoxide,        polyphosphoric acid, N,N′-carbodiimidazole,        2-ethoxy-N-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ),        triphenylphosphine/carbon tetrachloride or        bromo-tripyrrolidinophosphonium hexafluorophosphate may be        mentioned by way of examples.    -   The reaction according to step (ii) is if appropriate carried        out in a solvent selected from standard solvents which are inert        under the prevailing reaction conditions. Preference is given to        aliphatic, alicyclic or aromatic hydrocarbons, such as, for        example, petroleum ether, hexane, heptane, cyclohexane,        methylcyclohexane, benzene, toluene, xylene or decalin;        halogenated hydrocarbons, such as, for example, chlorobenzene,        dichlorobenzene, dichloromethane, chloroform, carbon        tetrachloride, dichloroethane or trichloroethane; ethers, such        as, for example, diethyl ether, diisopropyl ether, methyl        tert-butyl ether (MTBE), methyl tert-amyl ether, dioxane,        tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or        anisole; nitriles, such as, for example, acetonitrile,        propionitrile, n- or isobutyronitrile or benzonitrile; amides,        such as, for example, N,N-dimethylformamide (DMF),        N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone        (NMP) or hexamethylenephosphoric triamide; esters, such as, for        example, methyl acetate or ethyl acetate; sulfoxides, such as,        for example, dimethyl sulfoxide (DMSO); sulfones, such as, for        example, sulfolane; alcohols, such as, for example, methanol,        ethanol, n- or isopropanol, n-, iso-, sec- or tert-butanol,        ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol,        diethylene glycol monomethyl ether, diethylene glycol monoethyl        ether or mixtures of these.-   (iii) According to a further alternative embodiment according to the    invention shown in scheme (I) as step (iii), the aniline ethers of    the formula (VIII) are reacted with amines of the formula (XV) in    which the groups R² and R³ are as defined above in the presence of    ortho esters of the formula (XVI), in which R′ is as defined above    and R¹⁰ to R′² independently of one another are selected from the    group consisting of C₁₋₈-alkyl groups, preferably from C₂₋₆-alkyl    groups, particularly preferably from C₃₋₅-alkyl groups, to give the    4-substituted phenoxyphenylamidines according to the invention.    -   The reaction according to step (iii) is preferably carried out        in a solvent selected from standard solvents which are inert        under the prevailing reaction conditions. Preference is given to        aliphatic, alicyclic or aromatic hydrocarbons, such as, for        example, petroleum ether, hexane, heptane, cyclohexane,        methylcyclohexane, benzene, toluene, xylene or decalin;        halogenated hydrocarbons, such as, for example chlorobenzene,        dichlorobenzene, dichloromethane, chloroform, carbon        tetrachloride, dichloroethane or trichloroethane; ethers, such        as, for example, diethyl ether, diisopropyl ether, methyl        tert-butyl ether (MTBE), methyl tert-amyl ether, dioxane,        tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or        anisole; nitriles, such as, for example, acetonitrile,        propionitrile, n- or isobutyronitrile or benzonitrile; amides,        such as, for example, N,N-dimethylformamide (DMF),        N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone        (NMP) or hexamethylene phosphoric triamide; esters, such as, for        example, methyl acetate or ethyl acetate; sulfoxides, such as,        for example, dimethyl sulfoxide (DMSO); sulfones, such as, for        example, sulfolane; alcohols, such as, for example, methanol,        ethanol, n- or isopropanol, n-, iso-, sec- or tert-butanol,        ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol,        diethylene glycol monomethyl ether, diethylene glycol monoethyl        ether; or mixtures of these with water, and also pure water.        Step (g)

In an alternative embodiment according to the invention, it is alreadypossible to react the aminophenols or aminobenzoketones of the formula(XII)

-   (i) with amino acetals of the formula (XIII) or-   (ii) with amides of the formula (XIV) or-   (iii) with amines of the formula (XV) in the presence of ortho    esters of the formula (XVI)    in accordance with the reaction scheme below to give amidines of the    formula (X):

With regard to the reaction conditions, solvents, catalysts, referencemay be made to step (f).

The further conversion of the amidines of the formula (X) into thetarget molecules of the formula (I) according to the invention can becarried out, for example, as described in step (j).

Step (h)

In an alternative embodiment according to the invention, it is possibleto react the aminophenyl derivatives of the formula (VII)

-   (i) with amino acetals of the formula (XIII) or-   (ii) with amides of the formula (XIV) or-   (iii) with amines of the formula (XV) in the presence of ortho    esters of the formula (XVI)    in accordance with the reaction scheme below to give amidines of the    formula (XI):

With regard to the reaction conditions, solvents, catalysts, referencemay be made to step (f).

The further conversion of the amidines of the formula (XI) into thetarget molecules of the formula (I) according to the invention can becarried out, for example, as described in step (i).

Step (i)

According to a further embodiment according to the invention, theamidines of the formula (XI) obtainable from step (h) can be reactedwith dihalophenols of the formula (II) or the phenoxides formedtherefrom to give the target molecules of the formula (I) according tothe invention, in accordance with the reaction scheme below:

With regard to the reaction conditions, leaving groups (Z), solvents andcatalysts, reference may be made to step (a).

Step (j)

According to a further embodiment according to the invention, theamidines of the formula (X) obtainable from step (g) can be reacted with4-substituted phenyl derivatives of the formula (IV) to give the targetmolecules of the formula (I) according to the invention, in accordancewith the reaction scheme below:

With regard to the reaction conditions, solvents and catalysts,reference may be made to step (b).

In connection with the processes according to the invention forpreparing the amidines of the formula (I), the following combinations ofreaction steps are to be regarded as advantageous: steps (a), (e) and(f); steps (b), (e) and (f); steps (c) and (f); steps (d) and (f); steps(h) and (i) and/or steps (g) and (j).

The preparation of the phenoxyphenylamidines according to the inventionis preferably carried out without intermediate isolation of theintermediates.

The final purification of the phenoxyphenylamidines can be carried outusing customary purification methods. Preferably, purification iscarried out by crystallization.

Controlling of Undesirable Microorganisms

The amidines according to the invention exhibit a strong microbicidalaction and can be used for controlling undesirable microorganisms, suchas fungi and bacteria, in plant protection and in material protection.

Plant Protection

Fungicides can be used in plant protection for controllingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericides can be used in plant protection for controllingPseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceaeand Streptomycetaceae.

Mention may be made, by way of example but without limitation, of somepathogens of fungal and

-   bacterial diseases which come under the generic terms listed above:-   diseases caused by pathogens of powdery mildew, such as, for    example,-   Blumeria species, such as, for example, Blumeria graminis;-   Podosphaera species, such as, for example, Podosphaera leucotricha;-   Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;-   Uncinula species, such as, for example, Uncinula necator;-   diseases caused by rust pathogens, such as, e.g.,-   Gymnosporangium species, such as, for example, Gymnosporangium    sabinae;-   Hemileia species, such as, for example, Hemileia vastatrix;-   Phakopsora species, such as, for example, Phakopsora pachyrhizi and    Phakopsora meibomiae;-   Puccinia species, such as, for example, Puccinia recondita;-   Uromyces species, such as, for example, Uromyces appendiculatus;-   diseases caused by pathogens of the Oomycetes group, such as, e.g.,-   Bremia species, such as, for example, Bremia lactucae;-   Peronospora species, such as, for example, Peronospora pisi or P.    brassicae;-   Phytophthora species, such as, for example, Phytophthora infestans;-   Plasmopara species, such as, for example, Plasmopara viticola;-   Pseudoperonospora species, such as, for example, Pseudoperonospora    humuli or-   Pseudoperonospora cubensis;-   Pythium species, such as, for example, Pythium ultimum;-   leaf spot diseases and leaf wilts caused by, e.g.,-   Alternaria species, such as, for example, Alternaria solani;-   Cercospora species, such as, for example, Cercospora beticola;-   Cladosporium species, such as, for example, Cladosporium    cucumerinum;-   Cochliobolus species, such as, for example, Cochliobolus sativus-   (conidial form: Drechslera, syn: Helminthosporium);-   Colletotrichum species, such as, for example, Colletotrichum    lindemuthanium;-   Cycloconium species, such as, for example, Cycloconium oleaginum;-   Diaporthe species, such as, for example, Diaporthe citri;-   Elsinoe species, such as, for example, Elsinoe fawcettii;-   Gloeosporium species, such as, for example, Gloeosporium laeticolor;-   Glomerella species, such as, for example, Glomerella cingulata;-   Guignardia species, such as, for example, Guignardia bidwelli;-   Leptosphaeria species, such as, for example, Leptosphaeria maculans;-   Magnaporthe species, such as, for example, Magnaporthe grisea;-   Mycosphaerella species, such as, for example, Mycosphaerella    graminicola and Mycosphaerella fijiensis;-   Phaeosphaeria species, such as, for example, Phaeosphaeria nodorum;-   Pyrenophora species, such as, for example, Pyrenophora teres;-   Ramularia species, such as, for example, Ramularia collo-cygni;-   Rhynchosporium species, such as, for example, Rhynchosporium    secalis;-   Septoria species, such as, for example, Septoria apii;-   Typhula species, such as, for example, Typhula incarnata;-   Venturia species, such as, for example, Venturia inaequalis;-   root and stalk diseases caused by, e.g.,-   Corticium species, such as, for example, Corticium graminearum;-   Fusarium species, such as, for example, Fusarium oxysporum;-   Gaeumannomyces species, such as, for example, Gaeumannomyces    graminis;-   Rhizoctonia species, such as, for example, Rhizoctonia solani;-   Tapesia species, such as, for example, Tapesia acuformis;-   Thielaviopsis species, such as, for example, Thielaviopsis basicola;-   ear and panicle diseases (including maize cobs) caused by, e.g.,-   Alternaria species, such as, for example, Alternaria spp.;-   Aspergillus species, such as, for example, Aspergillus flavus;-   Cladosporium species, such as, for example, Cladosporium    cladosporioides;-   Claviceps species, such as, for example, Claviceps purpurea;-   Fusarium species, such as, for example, Fusarium culmorum;-   Gibberella species, such as, for example, Gibberella zeae;-   Monographella species, such as, for example, Monographella nivalis;-   diseases caused by smuts, such as, e.g.,-   Sphacelotheca species, such as, for example, Sphacelotheca reiliana;-   Tilletia species, such as, for example, Tilletia caries;-   Urocystis species, such as, for example, Urocystis occulta;-   Ustilago species, such as, for example, Ustilago nuda;-   fruit rot caused by, e.g.,-   Aspergillus species, such as, for example, Aspergillus flavus;-   Botrytis species, such as, for example, Botrytis cinerea;-   Penicillium species, such as, for example, Penicillium expansum and    Penicillium purpurogenum;-   Sclerotinia species, such as, for example, Sclerotinia sclerotiorum;-   Verticilium species, such as, for example, Verticilium alboatrum;-   seed- and soil-borne rots and wilts, and seedling diseases, caused    by, e.g.,-   Alternaria species, such as, for example, Alternaria brassicicola;-   Aphanomyces species, such as, for example, Aphanomyces euteiches;-   Ascochyta species, such as, for example, Ascochyta lentis;-   Aspergillus species, such as, for example, Aspergillus flavus;-   Cladosporium species, such as, for example, Cladosporium herbarum;-   Cochliobolus species, such as, for example, Cochliobolus sativus-   (conidial form: Drechslera, Bipolaris syn: Helminthosporium);-   Colletotrichum species, such as, for example, Colletotrichum    coccodes;-   Fusarium species, such as, for example, Fusarium culmorum;-   Gibberella species, such as, for example, Gibberella zeae;-   Macrophomina species, such as, for example, Macrophomina phaseolina;-   Monographella species, such as, for example, Monographella nivalis;-   Penicillium species, such as, for example, Penicillium expansum;-   Phoma species, such as, for example, Phoma lingam;-   Phomopsis species, such as, for example, Phomopsis sojae;-   Phytophthora species, such as, for example, Phytophthora cactorum;-   Pyrenophora species, such as, for example, Pyrenophora graminea;-   Pyricularia species, such as, for example, Pyricularia oryzae;-   Pythium species, such as, for example, Pythium ultimum;-   Rhizoctonia species, such as, for example, Rhizoctonia solani;-   Rhizopus species, such as, for example, Rhizopus oryzae;-   Sclerotium species, such as, for example, Sclerotium rolfsii;-   Septoria species, such as, for example, Septoria nodorum;-   Typhula species, such as, for example, Typhula incarnata;-   Verticillium species, such as, for example, Verticillium dahliae;-   cankers, galls and witches' broom disease caused by, e.g.,-   Nectria species, such as, for example, Nectria galligena;-   wilts caused by, e.g.,-   Monilinia species, such as, for example, Monilinia laxa;-   deformations of leaves, flowers and fruits caused by, e.g.,-   Taphrina species, such as, for example, Taphrina deformans;-   degenerative diseases of woody plants caused by, e.g.,-   Esca species, such as, for example, Phaeomoniella chlamydospora,    Phaeoacremonium aleophilum and Fomitiporia mediterranea;-   flower and seed diseases caused by, e.g.,-   Botrytis species, such as, for example, Botrytis cinerea;-   diseases of plant tubers caused by, e.g.,-   Rhizoctonia species, such as, for example, Rhizoctonia solani;-   Helminthosporium species, such as, for example, Helminthosporium    solani;-   diseases caused by bacterial pathogens, such as, e.g.,-   Xanthomonas species, such as, for example, Xanthomonas campestris    pv. oryzae;-   Pseudomonas species, such as, for example, Pseudomonas syringae pv.    lachrymans;-   Erwinia species, such as, for example, Erwinia amylovora.

Preferably, the following diseases of soybeans can be combated:

fungal diseases on leaves, stalks, pods and seeds caused by, e.g.,

alternaria leaf spot (Alternaria spec. atrans tenuissima), anthracnose(Colletotrichum gloeosporoides dematium var. truncatum), brown spot(Septoria glycines), cercospora leaf spot and blight (Cercosporakikuchii), choanephora leaf blight (Choanephora infundibulifera trispora(Syn.)), dactuliophora leaf spot (Dactuliophora glycines), downy mildew(Peronospora manshurica), drechslera blight (Drechslera glycini),frogeye leaf spot (Cercospora sojina), leptosphaerulina leaf spot(Leptosphaerulina trifolii), phyllostica leaf spot (Phyllostictasojaecola), pod and stem blight (Phomopsis sojae), powdery mildew(Microsphaera diffusa), pyrenochaeta leaf spot (Pyrenochaeta glycines),rhizoctonia aerial, foliage, and web blight (Rhizoctonia solani), rust(Phakopsora pachyrhizi), scab (Sphaceloma glycines), stemphylium leafblight (Stemphylium botryosum), target spot (Corynespora cassiicola)fungal diseases on roots and the stem base caused by, e.g.,black root rot (Calonectria crotalariae), charcoal rot (Macrophominaphaseolina), fusarium blight or wilt, root rot, and pod and collar rot(Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusariumequiseti), mycoleptodiscus root rot (Mycoleptodiscus terrestris),neocosmospora (Neocosmopspora vasinfecta), pod and stem blight(Diaporthe phaseolorum), stem canker (Diaporthe phaseolorum var.caulivora), phytophthora rot (Phytophthora megasperma), brown stem rot(Phialophora gregata), pythium rot (Pythium aphanidermatum, Pythiumirregulare, Pythium debaryanum, Pythium myriotylum, Pythium ultimum),rhizoctonia root rot, stem decay, and damping-off (Rhizoctonia solani),sclerotinia stem decay (Sclerotinia sclerotiorum), sclerotinia southernblight (Sclerotinia rolfsii), thielaviopsis root rot (Thielaviopsisbasicola).

The active compounds according to the invention also exhibit a strongstrengthening activity in plants. They are accordingly suitable formobilizing intrinsic defenses of plants against attack by undesirablemicroorganisms.

In the present context, plant-strengthening (resistance-inducing)compounds are to be understood as meaning those materials which arecapable of stimulating the defense system of plants such that thetreated plants, on subsequent inoculation with undesirablemicroorganisms, exhibit extensive resistance to these microorganisms.

In the present case, undesirable microorganisms are to be understood asmeaning phytopathogenic fungi, bacteria and viruses. The substancesaccording to the invention can thus be used to protect plants fromattack by the harmful pathogens mentioned for a certain period of timeafter the treatment. The period of time for which protection is broughtabout generally ranges from 1 to 10 days, preferably 1 to 7 days, afterthe treatment of the plants with the active compounds.

The fact that the active compounds are well tolerated by plants in theconcentrations necessary for controlling plant diseases makes possibletreatment of above ground plant parts, of plant propagation material andseed, and of the soil.

In this connection, the active compounds according to the invention canbe used particularly successfully in controlling cereal diseases, suchas, e.g., Puccinia species, and diseases in viticulture and in thecultivation of fruit and vegetables, such as, e.g., Botrytis, Venturiaor Alternaria species.

The active compounds according to the invention are also suitable forincreasing the crop yield. In addition, they are of lower toxicity andare well tolerated by plants.

The active compounds according to the invention can also optionally beused, in specific concentrations and application amounts, as herbicides,for affecting plant growth and for controlling animal pests. They canoptionally also be used as intermediates and precursors for thesynthesis of additional active compounds.

All plants and plant parts can be treated according to the invention. Inthis connection, plants are to be understood as meaning all plants andplant populations, such as desirable and undesirable wild plants orcultivated plants (including naturally occurring cultivated plants).Cultivated plants can be plants which can be obtained by conventionalbreeding and optimization methods or by biotechnological and geneticengineering methods or combinations of these methods, includingtransgenic plants and including plant varieties which may or may not beprotected by laws on variety certification. Plant parts should beunderstood as meaning all above ground and subsoil parts and organs ofplants, such as shoot, leaf, flower and root, examples which are listedbeing leaves, needles, stalks, stems, flowers, fruiting bodies, fruitsand seeds, and also roots, tubers and rhizomes. Plant parts also includeharvested crops, and also vegetative and generative propagationmaterial, for example cuttings, tubers, rhizomes, slips and seeds.

The treatment according to the invention of the plants and plant partswith the active compounds is carried out directly or by acting on theenvironment, habitat or storage area thereof using conventionaltreatment methods, e.g. by dipping, spraying, evaporating, atomizing,scattering, spreading and, with propagation material, in particular withseeds, furthermore by coating with one or more layers.

Mycotoxins

In addition, it is possible, by the treatment according to theinvention, to reduce the mycotoxin content in harvested crops and thefoodstuffs and feedstuffs prepared therefrom. In this connection,mention may in particular but not exclusively be made of the followingmycotoxins: deoxynivalenol (DON), nivalenol, 15-Ac-DON, 3-Ac-DON, T2 andHT2 toxin, fumonisins, zearalenone, moniliformin, fusarin,diacetoxyscirpenol (DAS), beauvericin, enniatin, fusaroproliferin,fusarenol, ochratoxins, patulin, ergot alkaloids and aflatoxins, whichcan be caused, for example, by the following fungi: Fusarium spec., suchas Fusarium acuminatum, F. avenaceum, F. crookwellense, F. culmorum, F.graminearum (Gibberella zeae), F. equiseti, F. fujikoroi, F. musarum, F.oxysporum, F. proliferatum, F. poae, F. pseudograminearum, F.sambucinum, F. scirpi, F. semitectum, F. solani, F. sporotrichoides, F.langsethiae, F. subglutinans, F. tricinctum, F. verticillioides, andothers, and also by Aspergillus spec., Penicillium spec., Clavicepspurpurea, Stachybotrys spec., and others.

Material Protection

In material protection, the substances according to the invention can beused for the protection of industrial materials from attack anddestruction by undesirable microorganisms.

Industrial materials are to be understood in the present context asmeaning nonliving materials which have been prepared for use inindustry. For example, industrial materials which are to be protected byactive compounds according to the invention from microbial change ordestruction can be adhesives, sizes, paper and board, textiles, leather,wood, paints and plastic articles, cooling lubricants and othermaterials which can be attacked or destroyed by microorganisms. In thecontext of the materials to be protected, mention may also be made ofparts of production plants, for example cooling water circuits, whichcan be detrimentally affected by proliferation of microorganisms. In thecontext of the present invention, mention may preferably be made, asindustrial materials, of adhesives, sizes, papers and boards, leather,wood, paints, cooling lubricants and heat-transfer liquids, particularlypreferably of wood.

Examples which may be mentioned of microorganisms which can decompose ormodify industrial materials are bacteria, fungi, yeasts, algae and slimeorganisms. The active compounds according to the invention arepreferably active against fungi, in particular molds, wood-discoloringand wood-destroying fungi (Basidiomycetes), and against slime organismsand algae.

Mention may be made, by way of example, of microorganisms of thefollowing genera:

Alternaria, such as Alternaria tenuis,

-   Aspergillus, such as Aspergillus niger,-   Chaetomium, such as Chaetomium globosum,-   Coniophora, such as Coniophora puetana,-   Lentinus, such as Lentinus tigrinus,-   Penicillium, such as Penicillium glaucum,-   Polyporus, such as Polyporus versicolor,-   Aureobasidium, such as Aureobasidium pullulans,-   Sclerophoma, such as Sclerophoma pityophila,-   Trichoderma, such as Trichoderma viride,-   Escherichia, such as Escherichia coli,-   Pseudomonas, such as Pseudomonas aeruginosa,-   Staphylococcus, such as Staphylococcus aureus.    Formulations

The present invention relates to a composition for controllingundesirable microorganisms, comprising at least one of thephenoxyphenylamidines according to the invention.

The phenoxyphenylamidines according to the invention can for this,depending on their respective physical and/or chemical properties, beconverted into the standard formulations, such as solutions, emulsions,suspensions, powders, foams, pastes, granules, aerosols, very fineencapsulations in polymeric substances and in coating materials forseed, and also ULV cold- and hot-fogging formulations.

These formulations are prepared in a known way, e.g. by mixing theactive compounds with extenders, that is liquid solvents, liquefiedgases under pressure and/or solid carriers, optionally with the use ofsurface-active agents, that is emulsifiers and/or dispersants and/orfoaming agents. In the case of the use of water as extender, use mayalso be made, e.g., of organic solvents as cosolvents. Possible liquidsolvents are essentially: aromatic hydrocarbons, such as xylene, tolueneor alkylnaphthalenes, chlorinated aromatic hydrocarbons or chlorinatedaliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes ormethylene chloride, aliphatic hydrocarbons, such as cyclohexane orparaffins, e.g. petroleum fractions, alcohols, such as butanol orglycol, and the ethers and esters thereof, ketones, such as acetone,methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, stronglypolar solvents, such as dimethylformamide and dimethyl sulfoxide, andalso water. Liquefied gaseous extenders or carriers are to be understoodas meaning those liquids which are in the gas form at standardtemperature and at standard pressure, e.g. aerosol propellants, such ashalogenated hydrocarbons and also butane, propane, nitrogen and carbondioxide. Possible solid carriers are, e.g., ground natural minerals,such as kaolins, argillaceous earths, talc, chalk, quartz, attapulgite,montmorillonite or diatomaceous earth, and ground synthetic minerals,such as highly dispersed silica, aluminum oxide and silicates. Possiblesolid carriers for granules are, e.g., broken and fractionated naturalrocks, such as calcite, pumice, marble, sepiolite or dolomite, and alsosynthetic granules formed from inorganic and organic dusts, and alsogranules formed from organic material, such as sawdust, coconut shells,maize cobs and tobacco stalks. Possible emulsifiers and/or foamingagents are, e.g., nonionic and anionic emulsifiers, such aspolyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers,e.g. alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates,arylsulfonates, and also protein hydrolyzates. Possible dispersants are,e.g., lignosulfite waste liquors and methylcellulose.

Use may be made, in the formulations, of stickers, such ascarboxymethylcellulose, natural and synthetic polymers in the powder,granule or latex form, such as gum arabic, polyvinyl alcohol, polyvinylacetate, and also natural phospholipids, such as cephalins andlecithins, and synthetic phospholipids. Other possible additives aremineral and vegetable oils.

Use may also be made of colorants, such as inorganic pigments, e.g. ironoxide, titanium oxide, Prussian blue, and organic colorants, such asalizarin dyes, azo dyes and metal phthalocyanine dyes, and traceelements, such as salts of iron, manganese, boron, copper, cobalt,molybdenum and zinc.

The formulations generally comprise between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

The formulations described above can be used in a method according tothe invention for controlling undesirable microorganisms, in which thephenoxyphenylamidines according to the invention are applied to themicroorganisms and/or to the habitat thereof.

Seed Treatment

The controlling of phytopathogenic fungi by the treatment of the seed ofplants has been known for a long time and is the subject matter ofcontinuous improvements. Nevertheless, a series of problems arises inthe treatment of seed, which problems may not always be satisfactorilysolved. Thus, it is desirable to develop methods for protecting the seedand the germinating plant which render superfluous or at least markedlyreduce the additional application of plant protection compositions aftersowing or after emergence of the plants. It is furthermore desirable tooptimize the amount of the active compound used, so that the seed andthe germinating plant are given the best possible protection againstattack by phytopathogenic fungi but without the plant itself beingdamaged by the active compound used. In particular, methods for thetreatment of seed should also include the intrinsic fungicidalproperties of transgenic plants in order to achieve optimum protectionof the seed and the germinating plant with a minimum expenditure ofplant protection compositions.

The present invention therefore also relates in particular to a methodfor the protection of seed and germinating plants from attack byphytopathogenic fungi, by treating the seed with a composition accordingto the invention.

The invention likewise relates to the use of the compositions accordingto the invention for the treatment of seed to protect the seed and thegerminating plant from phytopathogenic fungi.

Furthermore, the invention relates to seed which has been treated with acomposition according to the invention in order to protect fromphytopathogenic fungi.

One of the advantages of the present invention is that, because of theparticular systemic properties of the compositions according to theinvention, the treatment of the seed with these compositions not onlyprotects the seed itself from phytopathogenic fungi but also protectsthe plants resulting therefrom after emergence from phytopathogenicfungi. In this way, the immediate treatment of the crop at the time ofsowing or shortly thereafter can be dispensed with.

It is likewise to be regarded as advantageous that the mixturesaccording to the invention can in particular also be used withtransgenic seed.

The compositions according to the invention are suitable for theprotection of seed of any plant variety used in agriculture, in thegreenhouse, in forests or in horticulture. The seed concerned in thisconnection is in particular seed of cereals (such as wheat, barley, rye,millet and oats), maize, cotton, soya, rice, potatoes, sunflowers,beans, coffee, beet (e.g., sugarbeet and forage beet), peanuts,vegetables (such as tomatoes, cucumbers, onions and lettuce), lawns andornamental plants. The treatment of the seed of cereals (such as wheat,barley, rye and oats), maize and rice is of particular importance.

In the context of the present invention, the composition according tothe invention is applied to the seed alone or in a suitable formulation.Preferably, the seed is treated in a condition sufficiently stable forno damage to occur during the treatment. In general, the treatment ofthe seed can be carried out at any point in time between harvesting andsowing. Use is usually made of seed which has been separated from theplant and freed from pods, shells, stalks, skins, hairs or fruit flesh.Thus, it is possible, for example, to use seed which has been harvested,cleaned and dried up to a moisture content of less than 15% by weight.Alternatively, it is also possible to use seed which, after drying, hasbeen treated, e.g. with water, and then dried again.

In general, care must be taken, in the treatment of the seed, that theamount of the composition according to the invention and/or ofadditional additives applied to the seed is chosen so that thegermination of the seed is not impaired or that the plant resultingtherefrom is not damaged. This is to be taken into consideration inparticular with active compounds which may show phytotoxic effects atcertain application rates.

The compositions according to the invention can be applied immediately,thus without comprising additional components and without having beendiluted. It is generally preferable to apply the compositions to theseed in the form of a suitable formulation. Suitable formulations andmethods for seed treatment are known to a person skilled in the art andare described, e.g., in the following documents: U.S. Pat. Nos.4,272,417 A, 4,245,432 A,4,808,430 A, 5,876,739 A, US 2003/0176428 A1,WO 2002/080675 A1, WO 2002/028186 A2.

The active compound combinations which can be used according to theinvention can be converted into the usual seed dressing formulations,such as solutions, emulsions, suspensions, powders, foams, slurries orother coating materials for seed, and also ULV formulations.

These formulations are prepared in a known way by mixing the activecompounds or active compound combinations with conventional additives,such as, for example, conventional extenders and also solvents ordiluents, colorants, wetting agents, dispersants, emulsifiers,antifoaming agents, preservatives, secondary thickeners, adhesives,gibberellins and also water.

Suitable colorants which may be present in the seed dressingformulations which can be used according to the invention comprise allcolorants conventional for such purposes. In this connection, use may bemade both of pigments, which are sparingly soluble in water, and dyes,which are soluble in water. Mention may be made, as examples, of thecolorants known under the descriptions Rhodamine B, C.I. Pigment Red 112and C.I. Solvent Red 1.

Possible wetting agents which can be present in the seed dressingformulations which can be used according to the invention comprise allsubstances which promote wetting and are conventional in the formulationof agrochemical active compounds. Use may preferably be made ofalkylnaphthalenesulfonates, such as diisopropyl- ordiisobutylnaphthalenesulfonates.

Suitable dispersants and/or emulsifiers which may be present in the seeddressing formulations which can be used according to the inventioncomprise all nonionic, anionic and cationic dispersants conventional inthe formulation of agrochemical active compounds. Use may preferably bemade of nonionic or anionic dispersants or mixtures of nonionic oranionic dispersants. Mention may in particular be made, as suitablenonionic dispersants, of ethylene oxide/propylene oxide block polymers,alkylphenol polyglycol ethers and also tristyrylphenol polyglycolethers, and the phosphated or sulfated derivatives thereof. Suitableanionic dispersants are in particular lignosulfonates, polyacrylic acidsalts and arylsulfonate/formaldehyde condensates.

Antifoaming agents which may be present in the seed dressingformulations which can be used according to the invention comprise allfoam-inhibiting substances conventional in the formulation ofagrochemical active compounds. Use may preferably be made of siliconedefoaming agents and magnesium stearate.

Preservatives which may be present in the seed dressing formulationswhich can be used according to the invention comprise all substanceswhich can be used in agrochemical compositions for such purposes.Mention may be made, by way of example, of dichlorophen and benzylalcohol hemiformal.

Possible secondary thickeners which may be present in the seed dressingformulations which can be used according to the invention comprise allsubstances which can be used in agrochemical compositions for suchpurposes. Preferably suitable are cellulose derivatives, acrylic acidderivatives, xanthan, modified clays and highly dispersed silica.

Possible adhesives which may be present in the seed dressingformulations which can be used according to the invention comprise allconventional binders which can be used in seed dressings. Mention maypreferably be made of polyvinylpyrrolidone, polyvinyl acetate, polyvinylalcohol and tylose.

Possible gibberellins which may be present in the seed dressingformulations which can be used according to the invention preferablycomprise gibberellins A1, A3 (=gibberellic acid), A4 and A7; use isparticularly preferably made of gibberellic acid. Gibberellins are known(cf. R. Wegler, “Chemie der Pflanzenschutz- andSchädlingsbekämpfungsmittel” [Chemistry of Plant Protection and PestControl Agents], Vol. 2, Springer Verlag, 1970, pp. 401-412).

The seed dressing formulations which can be used according to theinvention can be used, either directly or after prior diluting withwater, for the treatment of seed of the most varied species. Thus, theconcentrates or the preparations which can be obtained therefrom bydiluting with water can be used for the dressing of the seed of cereals,such as wheat, barley, rye, oats and triticale, and also the seed ofmaize, rice, rape, peas, beans, cotton, sunflowers and beet, or also ofvegetable seed of the most varied natures. The seed dressingformulations which can be used according to the invention or the dilutedpreparations thereof can also be used for the dressing of seed oftransgenic plants. In this connection, additional synergistic effectsmay also occur in interaction with the substances formed by expression.

All mixing devices which can be conventionally used for dressing aresuitable for the treatment of seed with the seed dressing formulationswhich can be used according to the invention or the preparationsprepared therefrom by addition of water. Specifically, the dressingprocedure is such that the seed is introduced into a mixer, the amountof seed dressing formulation desired each time is added, either as suchor after prior dilution with water, and mixing is carried out until theformulation is uniformly distributed over the seed. If appropriate, adrying operation follows.

The application rate of the seed dressing formulations which can be usedaccording to the invention can be varied within a relatively wide range.It depends on the respective content of the active compounds in theformulations and on the seed. The application rates of active compoundcombination are generally between 0.001 and 50 g per kilogram of seed,preferably between 0.01 and 15 g per kilogram of seed.

Mixture with Known Fungicides, Bactericides, Acaricides, Nematicides orInsecticides

The phenoxyphenylamidines according to the invention can be used, assuch or in their formulations, also in a mixture with known fungicides,bactericides, acaricides, nematicides or insecticides, in order thus,e.g., to broaden the spectrum of activity or to prevent the developmentof resistance.

A mixture with other known active compounds, such as herbicides, or withfertilizers and growth regulators, safeners or semiochemicals is alsopossible.

In addition, the compounds of the formula (I) according to the inventionalso exhibit very good antimycotic activities. They have a very broadspectrum of antimycotic activity, in particular against dermatophytesand budding fungi, molds and diphasic fungi (e.g. against Candidaspecies, such as Candida albicans, Candida glabrata), and alsoEpidermophyton floccosum, Aspergillus species, such as Aspergillus nigerand Aspergillus fumigatus, Trichophyton species, such as Trichophytonmentagrophytes, Microsporon species, such as Microsporon canis andaudouinii. The enumeration of these fungi does not represent in any waya limitation on the mycotic spectrum which can be included but has onlyan illustrative nature.

The active compounds according to the invention can accordingly be usedboth in medicinal and in nonmedicinal applications.

The active compounds can be applied as such, in the form of theirformulations or in the form of the application forms prepared therefrom,such as ready-to-use solutions, suspensions, sprayable powders, pastes,soluble powders, dusts and granules. Application takes place in standardfashion, e.g. by pouring, spraying, atomizing, scattering, dusting,foaming, spreading, and the like. It is furthermore possible to applythe active compounds by the ultra-low-volume method or to inject theactive compound preparation or the active compound itself into the soil.

The seed of the plant can also be treated.

When the phenoxyphenylamidines according to the invention are used asfungicides, the application rates can be varied within a relatively widerange depending on the type of application. In the treatment of plantparts, the application rates of active compound are generally between0.1 and 10 000 g/ha, preferably between 10 and 1000 g/ha. In seedtreatment, the application rates of active compound are generallybetween 0.001 and 50 g per kilogram of seed, preferably between 0.01 and10 g per kilogram of seed. In soil treatment, the application rates ofactive compound are generally between 0.1 and 10 000 g/ha, preferablybetween 1 and 5000 g/ha.

GMOs

The method of treatment according to the invention can be used in thetreatment of genetically modified organisms (GMOs), e.g. plants orseeds. Genetically modified plants (or transgenic plants) are plants inwhich a heterologous gene has been stably integrated into the genome.The expression “heterologous gene” essentially means a gene which isprovided or assembled outside the plant and when introduced in thenuclear, chloroplastic or hypoochondrial genome gives the transformedplant new or improved agronomic or other properties by expressing aprotein or polypeptide of interest or by downregulating or silencingother gene(s) which are present in the plant (using, for example,antisense technology, cosuppression technology or RNA interference—RNAitechnology). A heterologous gene that is located in the genome is alsocalled a transgene. A transgene that is defined by its particularlocation in the plant genome is called a transformation or transgenicevent.

Depending on the plant species or plant cultivars, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the active compounds and compositions which can be usedaccording to the invention, better plant growth, increased tolerance tohigh or low temperatures, increased tolerance to drought or to water orsoil salt content, increased flowering performance, easier harvesting,accelerated maturation, higher harvest yields, bigger fruits, largerplant height, greener leaf color, earlier flowering, higher qualityand/or a higher nutritional value of the harvested products, highersugar concentration within the fruits, better storage stability and/orprocessability of the harvested products are possible, which exceed theeffects which were actually to be expected.

At certain application rates, the active compound combinations accordingto the invention may also have a strengthening effect in plants.Accordingly, they are suitable for mobilizing the defense system of theplant against attack by unwanted phytopathogenic fungi and/ormicroorganisms and/or viruses. This may, if appropriate, be one of thereasons for the enhanced activity of the combinations according to theinvention, for example against fungi. Plant-strengthening(resistance-inducing) substances are to be understood as meaning, in thepresent context, those substances or combinations of substances whichare capable of stimulating the defense system of plants in such a waythat, when subsequently inoculated with unwanted phytopathogenic fungiand/or microorganisms and/or viruses, the treated plants display asubstantial degree of resistance to these unwanted phytopathogenic fungiand/or microorganisms and/or viruses. In the present case, unwantedphytopathogenic fungi and/or microorganisms and/or viruses are to beunderstood as meaning phytopathogenic fungi, bacteria and viruses. Thus,the substances according to the invention can be employed for protectingplants against attack by the abovementioned pathogens within a certainperiod of time after the treatment. The period of time within whichprotection is effected generally extends from 1 to 10 days, preferably 1to 7 days, after the treatment of the plants with the active compounds.

Plants and plant cultivars which are preferably treated according to theinvention include all plants which have genetic material which impartsparticularly advantageous, useful traits to these plants (whetherobtained by breeding and/or biotechnological means).

Plants and plant cultivars which are also preferably treated accordingto the invention are resistant against one or more biotic stresses, i.e.the said plants show a better defense against animal and microbialpests, such as against nematodes, insects, mites, phytopathogenic fungi,bacteria, viruses and/or viroids.

Plants and plant cultivars which may also be treated according to theinvention are those plants which are resistant to one or more abioticstresses. Abiotic stress conditions may include, for example, drought,cold temperature exposure, heat exposure, osmotic stress, flooding,increased soil salinity, increased mineral exposure, ozone exposure,high light exposure, limited availability of nitrogen nutrients, limitedavailability of phosphorus nutrients, shade avoidance.

Plants and plant cultivars which may also be treated according to theinvention are those plants characterized by enhanced yieldcharacteristics. Increased yield in the said plants can be the resultof, for example, improved plant physiology, growth and development, suchas water use efficiency, water retention efficiency, improved nitrogenuse, enhanced carbon assimilation, improved photosynthesis, increasedgermination efficiency and accelerated maturation. Yield can furthermorebe affected by improved plant architecture (under stress and non-stressconditions), including early flowering, flowering control for hybridseed production, seedling vigor, plant size, internode number anddistance, root growth, seed size, fruit size, pod size, pod or earnumber, seed number per pod or ear, seed mass, enhanced seed filling,reduced seed dispersal, reduced pod dehiscence and lodging resistance.Further yield traits include seed composition, such as carbohydratecontent, protein content, oil content and composition, nutritionalvalue, reduction in anti-nutritional compounds, improved processabilityand better storage stability.

Plants that may be treated according to the invention are hybrid plantsthat already express the characteristics of heterosis or hybrid vigorwhich results in generally higher yield, vigor, health and resistancetowards biotic and abiotic stress factors. Such plants are typicallymade by crossing an inbred male-sterile parent line (the female parent)with another inbred male-fertile parent line (the male parent). Hybridseed is typically harvested from the male sterile plants and sold togrowers. Male sterile plants can sometimes (e.g. in maize) be producedby detasseling (i.e. the mechanical removal of the male reproductiveorgans or male flowers) but, more typically, male sterility is theresult of genetic determinants in the plant genome. In that case, andespecially when seed is the desired product to be harvested from thehybrid plants, it is typically useful to ensure that male fertility inhybrid plants that contain the genetic determinants responsible for malesterility is fully restored. This can be accomplished by ensuring thatthe male parents have appropriate fertility restorer genes which arecapable of restoring the male fertility in hybrid plants that containthe genetic determinants responsible for male sterility. Geneticdeterminants for male sterility may be located in the cytoplasm.Examples of cytoplasmic male sterility (CMS) were for instance describedin Brassica species (WO 1992/005251, WO 1995/009910, WO 1998/27806, WO2005/002324, WO 2006/021972 and U.S. Pat. No. 6,229,072). However,genetic determinants for male sterility can also be located in thenuclear genome. Male sterile plants can also be obtained by plantbiotechnology methods, such as genetic engineering. A particularlyuseful means of obtaining male-sterile plants is described in WO89/10396 in which, for example, a ribonuclease, such as a barnase, isselectively expressed in the tapetum cells in the stamens. Fertility canthen be restored by expression in the tapetum cells of a ribonucleaseinhibitor, such as barstar (e.g. WO 1991/002069).

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may be treated according to the inventionare herbicide-tolerant plants, i.e. plants made tolerant to one or moregiven herbicides. Such plants can be obtained either by genetictransformation, or by selection of plants containing a mutationimparting such herbicide tolerance.

Herbicide-tolerant plants are for example glyphosate-tolerant plants,i.e. plants made tolerant to the herbicide glyphosate or salts thereof.For example, glyphosate-tolerant plants can be obtained by transformingthe plant with a gene encoding the enzyme5-enolpyruvylshikimate-3-phosphate synthase (EPSPS). Examples of suchEPSPS genes are the AroA gene (mutant CT7) of the bacterium Salmonellatyphimurium (Comai et al., Science (1983), 221, 370-371), the CP4 geneof the bacterium Agrobacterium sp. (Barry et al., Curr. Topics PlantPhysiol. (1992), 7, 139-145), the genes encoding a petunia EPSPS (Shahet al., Science (1986), 233, 478-481), a tomato EPSPS (Gasser et al., J.Biol. Chem. (1988), 263, 4280-4289) or an eleusine EPSPS (WO2001/66704). It can also be a mutated EPSPS as described in for exampleEP-A 0837944, WO 2000/066746, WO 2000/066747 or WO 2002/026995.Glyphosate-tolerant plants can also be obtained by expressing a genethat encodes a glyphosate oxidoreductase enzyme as described in U.S.Pat. Nos. 5,776,760 and 5,463,175. Glyphosate-tolerant plants can alsobe obtained by expressing a gene that encodes a glyphosate acetyltransferase enzyme as described in for example WO 2002/036782, WO2003/092360, WO 2005/012515 and WO 2007/024782. Glyphosate-tolerantplants can also be obtained by selecting plants containingnaturally-occurring mutations of the above-mentioned genes, as describedin for example WO 2001/024615 or WO 2003/013226.

Other herbicide-resistant plants are for example plants that are madetolerant to herbicides inhibiting the enzyme glutamine synthase, such asbialaphos, phosphinotricin or glufosinate. Such plants can be obtainedby expressing an enzyme detoxifying the herbicide or a mutant of theglutamine synthase enzyme that is resistant to inhibition. One suchefficient detoxifying enzyme is an enzyme encoding a phosphinotricinacetyltransferase (such as the bar or pat protein from Streptomycesspecies). Plants expressing an exogenous phosphinotricinacetyltransferase are for example described in U.S. Pat. Nos. 5,561,236;5,648,477; 5,646,024; 5,273,894; 5,637,489; 5,276,268; 5,739,082;5,908,810 and 7,112,665.

Further herbicide-tolerant plants are also plants that are made tolerantto the herbicides inhibiting the enzyme hydroxyphenylpyruvatedioxygenase(HPPD). Hydroxyphenylpyruvatedioxygenases are enzymes that catalyze thereaction in which para-hydroxyphenylpyruvate (HPP) is transformed intohomogentizate. Plants tolerant to HPPD inhibitors can be transformedwith a gene encoding a naturally occurring resistant HPPD enzyme, or agene encoding a mutated HPPD enzyme as described in WO 1996/038567, WO1999/024585 and WO 1999/024586. Tolerance to HPPD inhibitors can also beobtained by transforming plants with genes encoding certain enzymesenabling the formation of homogentizate despite the inhibition of thenative HPPD enzyme by the HPPD inhibitor. Such plants and genes aredescribed in WO 1999/034008 and WO 2002/36787. Tolerance of plants toHPPD inhibitors can also be improved by transforming plants with a geneencoding an enzyme prephenate dehydrogenase in addition to a geneencoding an HPPD-tolerant enzyme, as described in WO 2004/024928.

Further herbicide-resistant plants are plants that are made tolerant toacetolactate synthase (ALS) inhibitors. Known ALS inhibitors include,for example, sulfonylurea, imidazolinone, triazolopyrimidines,pyrimidinyloxy(thio)benzoates and/or sulfonylaminocarbonyltriazolinoneherbicides. Different mutations in the ALS enzyme (also known asacetohydroxyacid synthase, AHAS) are known to confer tolerance todifferent herbicides and groups of herbicides, as described for examplein Tranel and Wright, Weed Science (2002), 50, 700-712, but also in U.S.Pat. Nos. 5,605,011, 5,378,824, 5,141,870 and 5,013,659. The productionof sulfonylurea-tolerant plants and imidazolinone-tolerant plants isdescribed in U.S. Pat. Nos. 5,605,011; 5,013,659; 5,141,870; 5,767,361;5,731,180; 5,304,732; 4,761,373; 5,331,107; 5,928,937; and 5,378,824;and in international publication WO 1996/033270. Otherimidazolinone-tolerant plants are also described in, for example, WO2004/040012, WO 2004/106529, WO 2005/020673, WO 2005/093093, WO2006/007373, WO 2006/015376, WO 2006/024351 and WO 2006/060634. Furthersulfonylurea- and imidazolinone-tolerant plants are also described in,for example, WO 2007/024782.

Other plants tolerant to imidazolinone and/or sulfonylurea can beobtained by induced mutagenesis, selection in cell cultures in thepresence of the herbicide or by mutation breeding as described forexample for soybeans in U.S. Pat. No. 5,084,082, for rice in WO1997/41218, for sugarbeet in U.S. Pat. No. 5,773,702 and WO 1999/057965,for lettuce in U.S. Pat. No. 5,198,599, or for sunflower in WO2001/065922.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are insect-resistant transgenic plants, i.e. plants maderesistant to attack by certain target insects. Such plants can beobtained by genetic transformation, or by selection of plants containinga mutation imparting such insect resistance.

An “insect-resistant transgenic plant”, as used herein, includes anyplant containing at least one transgene comprising a coding sequenceencoding:

-   1) an insecticidal crystal protein from Bacillus thuringiensis or an    insecticidal portion thereof, such as the insecticidal crystal    proteins listed by Crickmore et al., Microbiology and Molecular    Biology Reviews (1998), 62, 807-813, updated by Crickmore et    al. (2005) at the Bacillus thuringiensis toxin nomenclature, online    at: http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/), or    insecticidal portions thereof, e.g. proteins of the Cry protein    classes Cry1Ab, Cry1Ac, Cry1F, Cry2Ab, Cry3Ae or Cry3Bb or    insecticidal portions thereof; or-   2) a crystal protein from Bacillus thuringiensis or a portion    thereof which is insecticidal in the presence of a second other    crystal protein from Bacillus thuringiensis or a portion thereof,    such as the binary toxin made up of the Cy34 and Cy35 crystal    proteins (Moellenbeck et al., Nat. Biotechnol. (2001), 19, 668-72;    Schnepf et al., Applied Environm. Microb. (2006), 71, 1765-1774); or-   3) a hybrid insecticidal protein comprising parts of two different    insecticidal crystal proteins from Bacillus thuringiensis, such as a    hybrid of the proteins of 1) above or a hybrid of the proteins of 2)    above, e.g. the Cry1A.105 protein produced by maize event MON98034    (WO 2007/027777); or-   4) a protein of any one of 1) to 3) above wherein some, particularly    1 to 10, amino acids have been replaced by another amino acid to    obtain a higher insecticidal activity to a target insect species,    and/or to expand the range of target insect species affected, and/or    because of changes induced in the encoding DNA during cloning or    transformation, such as the Cry3Bb1 protein in maize events MON863    or MON88017, or the Cry3A protein in maize event MIR 604;-   5) an insecticidal secreted protein from Bacillus thuringiensis or    Bacillus cereus, or an insecticidal portion thereof, such as the    vegetative insecticidal (VIP) proteins listed at    http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/vip.html,    e.g., proteins from VIP3Aa protein class; or-   6) a secreted protein from Bacillus thuringiensis or Bacillus cereus    which is insecticidal in the presence of a second secreted protein    from Bacillus thuringiensis or B. cereus, such as the binary toxin    made up of the VIP1A and VIP2A proteins (WO 1994/21795);-   7) a hybrid insecticidal protein comprising parts from different    secreted proteins from Bacillus thuringiensis or Bacillus cereus,    such as a hybrid of the proteins in 1) above or a hybrid of the    proteins in 2) above; or-   8) a protein of any one of 1) to 3) above wherein some, particularly    1 to 10, amino acids have been replaced by another amino acid to    obtain a higher insecticidal activity to a target insect species,    and/or to expand the range of target insect species affected, and/or    because of changes induced in the encoding DNA during cloning or    transformation (while still encoding an insecticidal protein), such    as the VIP3Aa protein in cotton event COT 102.

Of course, an insect-resistant transgenic plant, as used herein, alsoincludes any plant comprising a combination of genes encoding theproteins of any one of the above classes 1 to 8. In one embodiment, aninsect-resistant plant contains more than one transgene encoding aprotein of any one of the above classes 1 to 8, to expand the range oftarget insect species affected or to delay insect resistance developmentto the plants by using different proteins insecticidal to the sametarget insect species but having a different mode of action, such asbinding to different receptor binding sites in the insect.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are tolerant to abiotic stresses. Such plants can be obtainedby genetic transformation, or by selection of plants containing amutation imparting such stress resistance.

Particularly useful stress tolerance plants include:

-   a. plants which contain a transgene capable of reducing the    expression and/or the activity of the poly(ADP-ribose)polymerase    (PARP) gene in the plant cells or plants as described in WO    2000/004173 or EP 04077984.5 or EP 06009836.5;-   b. plants which contain a stress tolerance enhancing transgene    capable of reducing the expression and/or activity of the PARG    encoding genes of the plants or plant cells, as described e.g. in WO    2004/090140;-   c. plants which contain a stress tolerance enhancing transgene    coding for a plant-functional enzyme of the nicotinamide adenine    dinucleotide salvage biosynthesis pathway, including nicotinamidase,    nicotinate phosphoribosyltransferase, nicotinic acid mononucleotide    adenyltransferase, nicotinamide adenine dinucleotide synthetase or    nicotinamide phosphoribosyltransferase, as described, e.g., in EP    04077624.7 or WO 2006/133827 or PCT/EP07/002,433.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention show altered quantity, quality and/or storage stability of theharvested product and/or altered properties of specific ingredients ofthe harvested product such as:

-   1) transgenic plants which synthesize a modified starch, which in    its physical-chemical characteristics, in particular the amylose    content or the amylose/amylopectin ratio, the degree of branching,    the average chain length, the side chain distribution, the viscosity    behavior, the gelling strength, the starch grain size and/or the    starch grain morphology, is changed in comparison with the    synthesized starch in wild type plant cells or plants, so that this    modified starch is better suited for special applications. The said    transgenic plants synthesizing a modified starch are disclosed, for    example, in EP 0 571 427, WO 1995/004826, EP 0 719 338, WO    1996/15248, WO 1996/19581, WO 1996/27674, WO 1997/11188, WO    1997/26362, WO 1997/32985, WO 1997/42328, WO 1997/44472, WO    1997/45545, WO 1998/27212, WO 1998/40503, WO 99/58688, WO    1999/58690, WO 1999/58654, WO 2000/008184, WO 2000/008185, WO    2000/28052, WO 2000/77229, WO 2001/12782, WO 2001/12826, WO    2002/101059, WO 2003/071860, WO 2004/056999, WO 2005/030942, WO    2005/030941, WO 2005/095632, WO 2005/095617, WO 2005/095619, WO    2005/095618, WO 2005/123927, WO 2006/018319, WO 2006/103107, WO    2006/108702, WO 2007/009823, WO 2000/22140, WO 2006/063862, WO    2006/072603, WO 2002/034923, EP 06090134.5, EP 06090228.5, EP    06090227.7, EP 07090007.1, EP 07090009.7, WO 2001/14569, WO    2002/79410, WO 2003/33540, WO 2004/078983, WO 2001/19975, WO    1995/26407, WO 1996/34968, WO 1998/20145, WO 1999/12950, WO    1999/66050, WO 1999/53072, U.S. Pat. No. 6,734,341, WO 2000/11192,    WO 1998/22604, WO 1998/32326, WO 2001/98509, WO 2001/98509, WO    2005/002359, U.S. Pat. Nos. 5,824,790, 6,013,861, WO 1994/004693, WO    1994/009144, WO 1994/11520, WO 1995/35026 or WO 1997/20936.-   2) transgenic plants which synthesize nonstarch carbohydrate    polymers or which synthesize nonstarch carbohydrate polymers with    altered properties in comparison to wild type plants without genetic    modification. Examples are plants producing polyfructose, especially    of the inulin and levan type, as disclosed in EP 0 663 956, WO    1996/001904, WO 1996/021023, WO 1998/039460 and WO 1999/024593,    plants producing alpha-1,4-glucans as disclosed in WO 1995/031553,    US 2002/031826, U.S. Pat. Nos. 6,284,479, 5,712,107, WO 1997/047806,    WO 1997/047807, WO 1997/047808 and WO 2000/14249, plants producing    alpha-1,6 branched alpha-1,4-glucans, as disclosed in WO 2000/73422,    and plants producing alternan, as disclosed in WO 2000/047727, EP    06077301.7, U.S. Pat. No. 5,908,975 and EP 0 728 213.-   3) transgenic plants which produce hyaluronan, as for example    disclosed in WO 2006/032538, WO 2007/039314, WO 2007/039315, WO    2007/039316, JP 2006/304779 and WO 2005/012529.

Plants or plant cultivars (obtained by plant biotechnology methods, suchas genetic engineering) which may also be treated according to theinvention are plants, such as cotton plants, with altered fibercharacteristics. Such plants can be obtained by genetic transformation,or by selection of plants containing a mutation imparting such alteredfiber characteristics and include:

-   a) plants, such as cotton plants, containing an altered form of    cellulose synthase genes as described in WO 1998/000549,-   b) plants, such as cotton plants, containing an altered form of rsw2    or rsw3 homologous nucleic acids as described in WO 2004/053219;-   c) plants, such as cotton plants, with increased expression of    sucrose phosphate synthase as described in WO 2001/017333;-   d) plants, such as cotton plants, with increased expression of    sucrose synthase as described in WO 02/45485;-   e) plants, such as cotton plants, wherein the timing of the    plasmodesmatal gating at the basis of the fiber cell is altered,    e.g. through downregulation of fiber selective β-1,3-glucanase as    described in WO 2005/017157;-   f) plants, such as cotton plants, having fibers with altered    reactivity, e.g. through the expression of the N-acetylglucosamine    transferase gene including nodC and chitin synthase genes as    described in WO 2006/136351.

Plants or plant cultivars (obtained by plant biotechnology methods, suchas genetic engineering) which may also be treated according to theinvention are plants, such as oilseed rape or related Brassica plants,with altered oil profile characteristics. Such plants can be obtained bygenetic transformation or by selection of plants containing a mutationimparting such altered oil characteristics and include:

-   a) plants, such as oilseed rape plants, producing oil having a high    oleic acid content as described, e.g., in U.S. Pat. Nos. 5,969,169,    5,840,946, 6,323,392 or 6,063,947;-   b) plants such as oilseed rape plants, producing oil having a low    linolenic acid content as described in U.S. Pat. Nos. 6,270,828,    6,169,190 or 5,965,755;-   c) plants such as oilseed rape plants, producing oil having a low    level of saturated fatty acids as described, e.g., in U.S. Pat. No.    5,434,283.

Particularly useful transgenic plants which may be treated according tothe invention are plants which comprise one or more genes which encodeone or more toxins, are the transgenic plants which are sold under thefollowing trade names: YIELD GARD® (for example maize, cotton,soybeans), KnockOut® (for example maize), BiteGard® (for example maize),BT-Xtra® (for example maize), StarLink® (for example maize), Bollgard®(cotton), Nucotn® (cotton), Nucotn 33B® (cotton), NatureGard® (forexample maize), Protecta® and NewLeaf® (potato). Examples ofherbicide-tolerant plants which may be mentioned are maize varieties,cotton varieties and soybean varieties which are sold under thefollowing trade names: Roundup Ready® (tolerance to glyphosate, forexample maize, cotton, soybean), Liberty Link® (tolerance tophosphinotricin, for example oilseed rape), IMI® (tolerance toimidazolinone) and SCS® (tolerance to sulfonylurea), for example maize.Herbicide-resistant plants (plants bred in a conventional manner forherbicide tolerance) which may be mentioned include the varieties soldunder the name Clearfield® (for example maize).

Particularly useful transgenic plants which may be treated according tothe invention are plants containing transformation events, or acombination of transformation events, that are listed for example in thedatabases from various national or regional regulatory agencies (see forexample http://gmoinfo.jrc.it/gmp_browse.aspx andhttp://www.agbios.com/dbase.php).

The plants listed can be treated according to the invention in aparticularly advantageous manner with the compounds of the generalformula (I) and/or the active compound mixtures according to theinvention. The preferred ranges stated above for the active compounds ormixtures also apply to the treatment of these plants. Particularemphasis is given to the treatment of plants with the compounds ormixtures specifically mentioned in the present text.

The preparation and the use of the active compounds according to theinvention is intended to be more fully explained from the followingexamples without, however, being limited to these.

PREPARATION EXAMPLES Example 1N-Ethyl-N-methyl-N′-{4-[4-(4-methoxyphenyl)phenoxy]-2,5-dimethylphenyl}-formamidine

0.12 g (0.4 mmol) of 4-[4-(4-methoxyphenyl)phenoxy]-2,5-dimethylanilineis dissolved in 5 ml of toluene, and 0.25 ml of a solution ofN-ethyl-N-methylformamidine dimethyl acetal in methanol (60%) is added.The reaction mixture is stirred at 50° C. for 18 h and freed from thesolvent under reduced pressure. This gives 0.09 g of product (purity95.0%, yield 58.6%; log P (pH 2.3)=2.57).

Synthesis of the Starting Materials

4-[4-(4-Methoxyphenyl)phenoxy]-2,5-dimethylaniline

Under argon, 0.50 g (1.7 mmol) of 4-(4-bromophenoxy)-2,5-dimethylanilineand 0.34 g (2.2 mmol) of 4-methoxyphenylboronic acid are dissolved in 10ml of 1-butanol and the solution is admixed with 2.23 g (6.8 mmol) ofcesium carbonate, 39.5 mg (0.03 mmol) oftetrakis(triphenylphosphine)palladium(0) and 2.5 ml of water. Thereaction mixture is stirred at 80° C. for 16 h, poured into water andextracted repeatedly with ethyl acetate. The combined organic phases aredried over Na₂SO₄ and filtered and the solvent is removed under reducedpressure. This is followed by purification by column chromatography(0.44 g, purity 99.0%, yield 79.7%, log P (pH 2.3)=3.06).

4-(4-Bromophenoxy)-2,5-dimethylaniline

A solution of 18.90 g (46.9 mmol) of4-(4-bromophenoxy)-2,5-dimethylnitrobenzene in 150 ml of dioxane and 150ml of hydrochloric acid is admixed with 31.77 g (140.8 mmol) of tin(II)chloride dihydrate at room temperature and the mixture is then refluxedfor 3.5 h. It is cooled to room temperature, neutralized with 10%strength aqueous sodium hydroxide solution and extracted repeatedly withethyl acetate, and the extracts are dried over Na₂SO₄ and filtered, andthe solvent is removed under reduced pressure. This is followed bypurification by column chromatography (8.10 g, purity 88.0%, yield51.9%, log P (pH 2.3)=2.88).

4-(4-Bromophenoxy)-2,5-dimethylnitrobenzene

37.5 g (216.7 mmol) of 4-bromophenol and 35.4 g (256.2 mmol) ofpotassium carbonate are suspended in 500 ml of N,N-dimethylformamide andthe suspension is stirred at room temperature for 1 h, before 36.6 g(197.0 mmol) of 4-chloro-2,5-dimethylnitrobenzene are added. The mixtureis subsequently stirred at 150° C. for 14 h, water is added, andrepeated extraction is carried out with ethyl acetate. The extracts aredried over Na₂SO₄ and filtered and the solvent is removed under reducedpressure. This is followed by purification by column chromatography(48.0 g, purity 91.0%, yield 68.8%, log P (pH 2.3)=4.86).

Example 2N-Ethyl-N-methyl-N′-[4-(4-cyclohexylphenoxy)-2,5-dimethylphenyl]formamidine

0.26 g (0.9 mmol) of 4-(4-cyclohexylphenyl)-2,5-dimethylaniline isdissolved in 5 ml of toluene, and 0.20 ml of a solution ofN-ethyl-N-methylformamidine dimethylacetal in methanol (60%) is added.The reaction mixture is stirred at 50° C. for 12 h and freed from thesolvent under reduced pressure. It is then purified by columnchromatography. This gives 0.32 g of product (purity 91.6%, yield 90.7%;log P (pH 2.3)=2.99).

Synthesis of the Starting Materials

4-(4-Cyclohexylphenoxy)-2,5-dimethylaniline

A solution of 0.49 g (1.5 mmol) of4-(4-cyclohexylphenoxy)-2,5-dimethylnitrobenzene in 7 ml of dioxane and7 ml of hydrochloric acid is admixed with 1.01 g (4.5 mmol) of tin(II)chloride dihydrate at room temperature and the mixture is then refluxedfor 2 h. It is cooled to room temperature, neutralized with aqueousNaHCO₃ and extracted repeatedly with dichloromethane, and the extractsare dried over Na₂SO₄ and filtered, and the solvent is removed underreduced pressure. This is followed by purification by columnchromatography (0.29 g, purity 95.2%, yield 61.5%, log P (pH 2.3)=4.25).

4-(4-Cyclohexylphenoxy)-2,5-dimethylnitrobenzene

5.81 g (33.0 mmol) of 4-cyclohexylphenol, 5.57 g (30.0 mmol) of4-chloro-2,5-dimethylnitrobenzene and 6.22 g (45.0 mmol) of potassiumcarbonate are suspended in 30 ml of N,N-dimethylformamide and thesuspension is stirred at 150° C. for 12 h. It is then poured intoice-water and the precipitate is isolated by filtration, washedrepeatedly with hexane and dried under reduced pressure (12.1 g, purity71.9%, yield 88.9%, log P (pH 2.3)=6.69).

TABLE II (I)

logP No. R¹ R² R³ R⁴ R⁵ R⁶ R⁷ acidic  1 H Et Me Me Me H 4′-Cl—Ph 2.95  2H Et Me Me Me H 4′-SO₂Et—Ph 2.06  3 H Et Me Me Me H 4′-CF₃—Ph 2.94  4 HEt Me Me Me H 4′-NMe₂—Ph 2.13  5 H Et Me Me Me H 4′-OMe—Ph 2.47  6 H EtMe Me Me H 4′-SMe—Ph 2.67  7 H Et Me Me Me H 4′-tBu—Ph 3.41  8 H Et MeMe Me H 4′-Me(C═O)—Ph 2.32  9 H Et Me Me Me CF₃ C₆H₁₁ 3.54 10 H Et Me MeMe H 4′-(n-Bu—O—N═CH)—Ph 3.51 11 H Et Me Me Me H 4′-F—Ph 2.69 12 H Et MeMe Me H 4′-(Me—O—N═CH)—Ph 2.75 13 H Et Me Me Me H 2′-Et—Ph 2.89 14 H EtMe Me Me H 2′-CF₃—Ph 2.77 15 H Et Me Me Me H 2′-iPr—Ph 3.06 16 H Et MeMe Me H 2′-Me—Ph 2.75 17 H Et Me Me Me H 2′-F—Ph 2.56 18 H Et Me Me Me H2′—CH₃(CO)—Ph 2.29 19 H Et Me Me Me H 2′-CH₃—O—Ph 2.49 20 H —(CH₂)₅— MeMe H 2′-CF₃—Ph 2.93 21 H —(CH₂)₅— Me Me H 2′-F—Ph 2.98 22 H —(CH₂)₅— MeMe H 2′-CH₃(C═O)—Ph 3.52 23 H —(CH₂)₅— Me Me H 2′-Et—Ph 3.34 24 H—(CH₂)₅— Me Me H 2′-Me—Ph 3.22 25 H —(CH₂)₅— Me Me H 2′-iPr—Ph 2.46 26 H—(CH₂)₅— Me Me H 2′-Cl—Ph 2.77 27 H Et Me Me Me H 2′-Cl—Ph 2.67 28 H—(CH₂)₅— Me Me H 2′-O—CH₂CH(CH₃)₂—Ph 3.44 29 H Et Me Me Me H2′-O—CH₂CH(CH₃)₂—Ph 3.14 30 H —(CH₂)₄— Me Me H 4′-Cl—Ph 2.62 31 H Et MeMe Me H Ph 2.64 32 H Et Me Me Me H C₅H₉ 2.87 33 H iPr Me Me Me H C₅H₉3.00 34 H —CH₂(CH₃)—(CH₂)₄— Me Me H C₅H₉ 3.22 35 H —CH₂(CH₃)—(CH₂)₄— MeMe H C₅H₉ 3.13 36 H Et Me Me Me Cl C₅H₉ 3.19 37 H Et Me Me Me CF₃ C₅H₉3.25 38 H Et Me Me Me H C₆H₁₁ 2.99 39 H Et Me Me Me H C₆H₁₁ 3.20 40 H—CH₂(CH₃)—(CH₂)₄— Me Me H C₆H₁₁ 3.61 41 H —(CH₂)₅— Me Me H C₆H₁₁ 3.46

Use Examples Example 1 Podosphaera Test (Apple)/Protective

Solvents: 24.5 parts by weight of acetone

-   -   24.5 parts by weight of dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with theactive compound preparation at the stated application rate. After thespray coating has dried on, the plants are inoculated with an aqueousspore suspension of the apple mildew pathogen Podosphaera leucotricha.The plants are then placed in a greenhouse at about 23° C. and arelative atmospheric humidity of about 70%.

Evaluation is carried out 10 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

In this test, the following compounds 32, 38, 33, 41, 1, 2, 3, 8, 7, 11,5, 6, 13, 14, 15, 16, 17, 18, 20, 22, 23, 24, 25, 26 and 27 according tothe invention (see Table II) show, at an active compound concentrationof 100 ppm, an efficacy of 70% or more.

Example 2 Sphaerotheca Test (Cucumber)/Protective

Solvents: 24.5 parts by weight of acetone

-   -   24.5 parts by weight of dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with theactive compound preparation at the stated application rate. After thespray coating has dried, the plants are inoculated with an aqueous sporesuspension of Sphaerotheca fuliginea. The plants are then placed in agreenhouse at about 23° C. and a relative atmospheric humidity of about70%.

Evaluation is carried out 7 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

In this test, the compounds 32, 38, 33, 35, 41, 1, 2, 3, 8, 7, 11, 5, 6,19, 13, 14, 15, 16, 17, 18, 20, 22, 23, 24, 25, 26 and 27 according tothe invention (see Table II) show, at an active compound concentrationof 100 ppm, an efficacy of 70% or more.

Example 3 Botrytis Test (Bean)/Protective

Solvents: 24.5 parts by weight of acetone

-   -   24.5 parts by weight of dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with theactive compound preparation at the stated application rate. After thespray coating has dried on, 2 small pieces of agar overgrown withBotrytis cinerea are placed on each leaf. The inoculated plants are thenplaced in a darkened chamber at about 20° C. and 100% relativeatmospheric humidity.

Two days after the inoculation the size of the infected spots on theleaves is evaluated. 0% means an efficacy which corresponds to that ofthe control, whereas an efficacy of 100% means that no infection isobserved.

In this test, the compounds 32, 38, 33, 35, 41, 1, 3, 7, 11, 5, 6, 19,13, 14, 15, 16, 17, 18, 20, 22, 23, 24, 25, 26 and 27 according to theinvention (see Table II) show, at an active compound concentration of250 ppm, an efficacy of 70% or more.

Example 4 Uromyces Test (Bean)/Protective

Solvents: 24.5 parts by weight of acetone

-   -   24.5 parts by weight of dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with theactive compound preparation at the stated application rate. After thespray coating has dried on, the plants are inoculated with an aqueousspore suspension of the bean rust pathogen Uromyces appendiculatus andthen remain in an incubation cabin at about 20° C. and 100% relativeatmospheric humidity for 1 day.

The plants are then placed in a greenhouse at about 21° C. and arelative atmospheric humidity of about 90%.

Evaluation is carried out 10 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

In this test, the compounds 32, 38, 33, 35, 41, 1, 2, 8, 11, 5, 6, 19,13, 16, 17, 18, 25 and 27 according to the invention (see Table II)show, at an active compound concentration of 10 ppm, an efficacy of 70%or more.

Example 5 Alternaria Test (Tomato)/Protective

Solvent: 49 parts by weight of N,N-dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young tomato plants are sprayed withthe active compound preparation at the stated application rate. One dayafter treatment, the plants are inoculated with a spore suspension ofAlternaria solani and then stand at 100% relative humidity and 20° C.for 24 h. The plants then stand at 96% relative atmospheric humidity anda temperature of 20° C.

Evaluation is carried out 7 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

In this test, the compounds 32, 36, 11, 19, 27 and 31 according to theinvention (see Table II) show, at an active compound concentration of500 ppm, an efficacy of 70% or more.

Example 6 Puccinia Test (Wheat)/Protective

Solvent: 50 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with theactive compound preparation at the stated application rate. After thespray coating has dried on, the plants are sprayed with a conidiasuspension of Puccinia recondita. The plants remain in an incubationcabin at 20° C. and 100% relative atmospheric humidity for 48 hours.

The plants are then placed in a greenhouse at a temperature of about 20°C. and a relative atmospheric humidity of 80% to promote the developmentof rust pustules.

Evaluation is carried out 10 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

In this test, the following compounds 32, 38, 33, 34, 35, 40, 41, 1, 2,3, 9, 11, 5, 6, 19, 13, 14, 15, 16, 17, 18, 20, 21, 23, 24, 26 and 27according to the invention (see Table II) show, at an active compoundconcentration of 1000 ppm, an efficacy of 70% or more.

The invention claimed is:
 1. A 4-cycloalkyl- or 4-aryl-substitutedaniline ether of the formula (VIII)

in which R⁴ and R⁵ independently of one another are selected from thegroup consisting of —X, —CN, —SH, —SR″, —OR″, —(C═O)—R″, straight-chain,branched C₁₋₁₂-alkyl, C₂₋₁₂-alkenyl, C₂-₁₂-alkynyl groups, cyclicC₃₋₈-alkyl, C₄₋₈-alkenyl, C₄₋₈-alkynyl groups or C₅₋₁₈-aryl,C₇₋₁₉-aralkyl and C₇₋₁₉-alkaryl groups, where in the ring system of allof the cyclic groups mentioned above one or more carbon atoms may bereplaced by heteroatoms selected from the group consisting of N, O, Pand S and all of the groups mentioned above may be substituted by one ormore groups selected from the group consisting of —R′, —X, —OR′, —SR′,—NR′₂, —SiR′₃, —COOR′, —CN and —CONR′₂, where R′ represents hydrogen ora C₁₋₁₂₋alkyl group, which may be substituted by one or more heteroatomsselected from the group consisting of N, O, P and S, and R″ represents aC₁₋₁₂-alkyl group, where in the ring system of all of the cyclic groupsmentioned above one or more carbon atoms may be replaced by heteroatomsselected from the group consisting of N, O, P and S; R⁶ is selected fromthe group consisting of halogen atoms and C₁₋₆-haloalkyl groups; R⁷ isselected from the group consisting of alicyclic C₃₋₁₂-alkyl,C₄₋₁₂-alkenyl, C₄₋₁₂-alkynyl groups and C₅₋₁₈-aryl, C₇₋₁₉-aralkyl andC₇₋₁₉-alkaryl groups, which may be substituted by one or more groupsselected from the group consisting of —R′, —X, —OR′, —SO₂—R′, —SR′,—NR′₂, —SiR′₃, —COOR′, —CN and —CONR′₂, where R′ has the above meaningsand where the C₅₋₁₈-aryl, C₇₋₁₉-aralkyl and C₇₋₁₉-alkaryl groups may besubstituted by one or more heteroatoms selected from the groupconsisting of N, O, P and S; wherein X is chlorine, bromine, fluorine,or iodine, and their salts.
 2. A compound of claim 1, wherein R⁴ and R⁵independently of one another are selected from the group consisting of—X straight-chain or branched, C₁₋₈-alkyl, and C₁₋₅-haloalkyl groups; R⁶is selected from the group consisting of fluorine, chlorine, bromine,CF₃ and CHF₂; R⁷ is selected from the group consisting of phenyl,cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, andcyclooctyl, which may be substituted by one or more groups selected fromthe group consisting of —R′, —X, —OR′, —SO₂—R′, —SR′, —NR′₂, —SiR′₃,—COOR′, —CN and —CONR′₂, and their salts.
 3. A compound of claim 1,wherein R⁴ and R⁵ are independently selected from the group consistingof Cl, F, CF₃, CF₂H and methyl groups.
 4. A compound of claim 1, whereinR⁷ is selected from the group consisting of phenyl, 4-chlorophenyl,4-ethylsulfonylphenyl, 4-trifluoromethylphenyl, 4-dimethylaminophenyl,4-methoxyphenyl, 4-tertbutylphenyl, 4-acetylphenyl, 4-fluorophenyl,2-ethylphenyl, 2-trifluoromethylphenyl, 2-isopropylphenyl,2-methylphenyl, 2-fluorophenyl, 2-acetylphenyl, 2-methoxyphenyl,2-chlorophenyl, 2-(2-methylpropoxy)phenyl, cyclopropyl, cyclohexyl,cycloheptyl, and cyclooctyl.
 5. A compound of clam 1, wherein R⁴ and R⁵are methyl.